Clatratos de agua y biomolculas

Antonio Snchez Ruiz y Antonio Heredia Que la molcula de agua es nica es algo que aprenden muy pronto los estudiantes de qumica y biologa. Sus extraordinarias y singulares propiedades fsicas y qumicas hacen de la misma un tema aparte. Su importancia a nivel estructural es enfatizada todava en muchos trabajos de investigacin actuales; por otro lado, puede afirmarse que todava desconocemos muchas caractersticas y propiedades de este lquido. Repasaremos en este artculo algunas investigaciones recientes sobre la estructura de agrupaciones discretas de molculas de agua y sobre cmo stas ayudan a comprender mejor el efecto de solvatacin acuosa de biomolculas. Algunos datos termodinmicos El calor de sublimacin del hielo a 0C es de 11,2 kcal/mol, de las cuales 1,4 representan la energa cintica de las molculas en estado de vapor; las 9,8 kcal/mol restantes suponen la energa requerida para romper los enlaces que mantienen unido al cristal de hielo. stos son enlaces de hidrgeno casi exclusivamente, puesto que las interacciones de van der Waals, fundamentales en los cristales orgnicos, se pueden despreciar debido a su pequea contribucin. Si comparamos este calor de sublimacin con el de fusin del agua, encontramos que este ltimo es casi 8 veces menor, lo que implica que la mayor parte de la estructura de enlaces de hidrgeno en el slido se mantiene tambin en el lquido. Adems, el alto calor especfico del agua lquida hay que atribuirlo a la dependencia con la temperatura de la energa de organizacin molecular, en lugar de a la energa de molculas individuales. Clculos realizados con algunos modelos tericos dan como resultado una energa de los enlaces de hidrgeno ms apropiada para un cambio de conformacin que para una reorganizacin de estos enlaces, por lo que se postula la existencia de agrupaciones discretas de molculas de agua unidas por enlace de hidrgeno, formando trmeros, tetrmeros y pentmeros, fundamentalmente [Science, 271: 929-933, (1996)]. Estructura de las agrupaciones (clusters) Para el dmero (H2O)2, la teora y los datos experimentales estn en buena concordancia; para el trmero, tetrmero y pentmero, clculos tericos ab-initio realizados con bases extensas, predicen estructuras planas en las que cada monmero acta como dador y aceptor de un solo enlace de hidrgeno, quedando el hidrgeno restante por encima o debajo del plano de la molcula. Para el heptmero y agrupaciones mayores, existe tendencia a formar estructuras tridimensionales (3D), siendo el hexmero una agrupacin o cluster intermedia entre una estructura cclica plana y una 3D. Estos clculos se ven respaldados por medidas llevadas a cabo mediante la espectroscopia de vibracin-rotacin de efecto tnel (VRT). Para las agrupaciones de trmero, tetrmero y pentmero, se encuentra que los niveles de energa siguen los patrones de un rotor simtrico (debido a la simetra de la estructura cclica). En el caso del tetrmero y pentmero se determinaron dos constantes rotacionales, suficientes para establecer sin ambigedades que las estructuras responsables del espectro eran las predichas por los clculos. El estudio del espectro del

hexmero permiti sugerir una estructura 3D tambin en buena concordancia con los clculos efectuados [Science, 271: 929-933, (1996)]. Solvatacin acuosa Uno de los objetivos ms importantes de estas investigaciones radica en elucidar los detalles del mecanismo de solvatacin, que en el caso del agua (hidratacin) es ms importante que en ningn otro disolvente. La explicacin de la naturaleza de esta solvatacin se ha resuelto en parte por el estudio de las agrupaciones o clusters que forma el agua. Recientemente se ha encontrado que al hidratar solutos hidrofbicos, las molculas de agua pasan de estar unidas por enlaces de hidrgeno y sin estructura fija, a formar icosaedros truncados que envuelven la estructura o dominio molecular hidrofbico. Estas estructuras icosadricas estn formadas por pentgonos y hexgonos en una relacin 8:1. El pentmero parece ser, pues, fundamental en los mecanismos de hidratacin de biomolculas, al proporcionar la curvatura necesaria para formar la "jaula" ordenada de molculas de agua que rodean los dominios y estructuras ms apolares, lo que se conoce como estructura de clatrato. La figura adjunta muesta una representacin esquemtica de una estructura de clatrato alrededor de cadenas hidrocarbonadas apolares. Estudios de rayos X han demostrado que la protena crambina tiene hendiduras hidrofbicas en las que 16 molculas de agua de hidratacin se organizan en una cpsula de pentgonos concatenados que rodea al grupo metilo de residuos de leucina. Un comportamiento similar se ha observado en otras protenas y en polmeros de DNA y, a medida que se incrementa la hidrofilia del soluto, existe una tendencia muy acusada a formar anillos de 6 y 7 miembros (la estructura 3D de stos evita que las molculas de agua se ordenen mucho y se cree una situacin energticamente desfavorable). Esto proporciona una explicacin estructural de por qu el cambio de entropa que determina el efecto hidrofbico es proporcional a la superficie del soluto (a mayor superficie encerrada, mayor orden que se produce en el disolvente y menor es la entropa de la disolucin). Sin embargo, las agrupaciones icosadricas de molculas de agua descritas distan mucho de ser regulares, dado que al estar rodeadas por molculas de agua libres, las continuas y rpidas fluctuaciones de stas en el seno del lquido hacen que se produzcan cambios estructurales constantes. Al tener el clatrato de disolvente un extremo abierto, las molculas de esa zona son ms susceptibles de ser arrancadas que las de una zona cerrada, por estar unidas con menos enlaces a la estructura. Por esta razn, la cadena hidrofbica de una molcula anfiptica, incapaz de generar una estructura completa de molculas de agua a su alrededor, no tiene las mismas propiedades que una cadena hidrocarbonada totalmente apolar. Es preciso destacar el comportamiento distinto de las molculas de agua que

hidratan la superficie externa de muchas protenas, las cuales construyen una matriz flexible que posibilita que las cadenas polipetdicas respondan de un modo eficaz al entorno qumico durante el plegamiento de la protena, durante los procesos de interaccin protenaprotena o en la interaccin enzima-sustrato. Estos mecanismos tambin pueden explicar la anmala capacidad calorfica asociada con el efecto hidrofbico (al diluir un soluto parcial o totalmente apolar en agua, la capacidad calorfica de la disolucin aumenta respecto al agua sola) puesto que la formacin de estas estructuras alrededor del soluto supone un aumento de la energa necesaria para aumentar la temperatura de la disolucin, al tener que romperse estructuras con ms cohesin que en el lquido puro. Antonio Snchez Ruiz es alumno de 3 de Qumicas y Antonio Heredia es Profesor Titular de Bioqumica en la Universidad de Mlaga

HI HI HI......

Reduction of Physiological Effects of Alcohol Abuse By Substitution of a Harmless Alcohol Surrogate Created by Application of a Spin Field
(c) Robert Neil Boyd

Robert Neil Boyd, Ph. D. Presented for consideration to: The National Institute of Health, Alcohol Abuse Center Abstract: It has been found through empirical experimentations that the spin field causes various properties of a vast array of materials to be transferred, with varying degrees of intensity and various degrees of impermanency, into other various materials. This is most dramatically demonstrated when application of the spin field transfers the inebriating properties of alcoholic beverages into pure deionized water. When this treated water is assayed, it is found to be chemically pure water, yet, when consumed, it has all the properties of an alcoholic beverage, with none of the damaging side effects, such as cellular damages, hangover, or a tendency to generate obesity. We find that this result is related to the memory property of water, and indeed to the memory of space itself, which memory is transferred by application of the spin field. It is suggested that further experimentation and clinical trials should be performed to investigate the possibility of applications of spin-altered water in alcohol abuse programs. Theory:

The spin field is described rigorously by R. M. Kiehn: [1] [2] [3] From a topological viewpoint, Maxwell's electrodynamics indicates that the concept of chirality is to be associated with a third rank tensor density of Topological Spin induced by the interaction of the 4 vector potentials {A, phi } and the field excitations (D, H). The distinct concept of helicity is to be associated with the third rank tensor field of Topological Torsion induced by the interaction of the 4 vector potentials and field intensities (E, B). The 4-divergence of the topological Spin is equal to the first Poincare Invariant of classical electromagnetism. The 4-divergence of the topological Torsion is equal to the second Poincare Invariant. On space-time domains where either Poincare Invariant is zero, the closed integrals of the Spin (respectively, Torsion) have values whose ratios are rational. That is, both the objects of topological torsion and topological spin can be quantized by the deRham theorems. However, when the 4-divergence of Topological Torsion is not zero, the second Poincare invariant, E B, is not zero, and parity is not conserved. New time dependent wave solutions to the classical homogeneous Maxwell equations in the vacuum have been found. These waves are not transverse; they exhibit both torsion and spin; they have finite magnetic helicity, a non-zero Poynting vector, E x H and a non zero second Poincare invariant, E dot B. Two, four component, rank 3 tensors, constructed on topological grounds, in terms of the Fields and Potentials, are used to define the concepts of Torsion and Spin, even in domains with plasma currents. The divergence of the spin pseudo vector generates the Poincare invariant equivalent to the Lagrangian of the field, B dot H -D dot E -(A dot J - rho phi). The divergence of the Torsion pseudo vector generates the second Poincare invariant, E dot B. The Poincare invariants have closed integrals, which are deformation invariants, and therefore can be used to define deformable coherent structures in a plasma. When the second Poincare invariant is non-zero, there can exist solutions that are not time-reversal invariant. Put in simpler terms, the spin field can be described as a series of propagating helical vortices observed as carrying a dense interstitial flux of an array of particles, possibly ranging down to the sub-quantum, in size. [4] This flux of particles and the spin field helices act together, in some not well understood manner, to temporarily copy the physical properties of substances into other substances. It is this flux of sub-quantum particles, which seems to be responsible for the copying ability of the spin field. In relation to positively charged particles, such as the proton, the motion of the spin field energy is directed from the periphery to the center. For negatively charged particles, the field is directed from the center to the periphery. A spin field disturbance moves along a helical path in space, with a propagation velocity which is typically, significantly less than the speed of light. Propagation velocity is determined by the longitudinal moment of the impulse, and those parameters of the environment which the change the density of the winding of the helix of the spin field. For the spin field created by the spin field generator, as designed by A. A. Shpilman in 1995, [5] the longitudinal momentum of the spin field impulse is equal to the impulse of a proton, with an energy of 300 electron-volts in air, and 3 electron-volts in ferrite. The spin field helices are very sensitive to the magnitude and direction of the magnetic vector potential. The helices are guided in the direction of the vector potential, but not in the direction of the magnetic field! Spin fields of protons are guided in the direction of the Poynting vector. The space between the spin field helices is saturated with particles, which are similar to the neutrino, having energy at rest of an electron-volt or less. These particles are apparent as threads, composing closed toroidal knot-like structures, having various rest masses, topologies, characteristic sizes, and a broad spectrum of resonant frequencies. Apparently, the rules of gas dynamics apply to the interstitial particles associated with the spin field helix. The spin field and the torsion field have only recently begun to be investigated in this country. However, spin and torsion fields have been studied globally for many years. These studies have been particularly intensive in Russia, where the spin and torsion fields have been investigated for

some 50 years. There is now a fairly substantial literature on the spin and torsion fields by some prominent physics researchers, such as H. Kleinert,[6] R. M. Keihn, [7] [8] [9] V. Poponin [10], J. Sarfatti [11] [12] [13], A. Jadczyk [14], A. A. Shpilman [15], A. Shipov [16], B. Page [17], A. Frolov [18], S-P Sirag [19], A. Akimov [20], T. Smith [21], and A. Mishin [22], to name only a few. For example, here are some excerpts from an article by Yu. V. Nachalov and A. N. Sokolov. They link a variety of related and unusual observations, over a 40 year period, to spin and torsion fields: The experimental results obtained by various researchers in the period 1950-1990 are discussed. Since all experimental results under consideration could not be explained in the framework of existing theories, these results were placed under the category of "experimentally observed phenomena." It is shown that all of the experiments considered here, have demonstrated a manifestation of spin-torsion interactions. Over the course of the 20th century, various investigations in different countries, representing a variety of professional interests, repeatedly reported the discovery of unusual phenomena that could not be explained in the framework of existing theories. Since these authors could not understand the physics of the observed phenomena, they were forced to give their own names to the fields, emanations and energies responsible for the creation of these phenomena. For instance, N. A. Kozyrev's "Time Emanation", W. Reich's "O-Emanation" or "Orgone", M. R. Blondlot's "N-Emanation", I. M. Shakhparonov's "Mon-Emanation", A. G. Gurvich's "Mitogenetic Emanation", A. L. Chizhevsky's "Z-Emanation", A. I. Veinik's "Chronal field" and "M-field", A. A. Deev's "D-field", Yu. V. Tszyan Kanchzhen's "Biofield", H. Moriyama's "X-agent", V. V. Lensky's "Multipolar Energy", "Radiesthesietic Emanations", "Shape Power", "Empty Waves", and "pseudomagnetism", H.A.Nieper's "gravity field energy", T.T.Brown's "electrogravitation", "fifth force", "antigravitation", and "free energy". This list can easily be continued... Experiment: Rather than involving ourselves exclusively with studies of the mathematical theory of the spin and torsions field, or getting involved with the more esoteric energetic properties of spin and torsion fields, we have initiated a series of empirical experiments designed to verify the properties of the spin field, and its effects on organic living matter, and on inorganic materials. We have been particularly interested in observations, which have shown that the spin field has the remarkable property of copying certain attributes of materials into other materials [23], and laboratory results which have shown that application of the spin field causes increases in the organization density of materials and structures, for example, hardening stainless steel by some 30% beyond all known hardening techniques [24]. Our spin field generation experimental apparatus has been imported from Russia, with the generous assistance of A. A. Shpilman. (See patent, Republic of Kazakhstan N5366, G01N23/00, Bull.N4, 15.10.97)

We have recently obtained a new, Model G, spin field generator:

This is the device we have been using in our most recent experiments. It has a more stable and powerful output than the previous models. There is also a three phase model, with the schematic as shown:

At this stage in our researches, the three phase device is not designated as a required apparatus, as the model G spin field generator has proven adequate. We set up an experiment to test whether the transference of the inebriating properties of alcohol, into water, could be accomplished, as claimed by some of the Russian investigators. Very simply, we placed a food-grade plastic-coated paper container filled with alcohol, on the vertical axis above a container filled with pure de-ionized water. We arranged the spin field generator on the vertical axis centered above both containers as in the diagram below, with the generator at G, the alcohol at R, the water at W, where the spin field is denoted by the light blue cone, A.

We irradiated the stack of containers for the recommended 10 minutes. We tested the water for purity. It was exactly as when we had put it in the container. We then drank the water. We were astounded to discover that the spin field treated water had an intoxicating effect! As the writer is inordinately sensitive to alcohol, he was surprised to discover that there were no observable side effects. This result was later duplicated with several volunteer test subjects, to ensure the objectivity of the results. These volunteers reported no hangover symptoms after having consumed enough of the water to be the equivalent of a respectable "shot" of an 80 proof liquor. Based on these limited trials, in this simple experimental sequence, we have determined that the inebriating properties of the alcohol were indeed transferred into the water, where the energetic signature of the alcohol was stored, as though a memory, with none of the toxic effects of actual alcohol. Discussions of Results: While this transference of the inebriating quality of alcohol into pure water might seem astounding, water memory is well known in the practices of homeopathy, but it is poorly understood how the homeopathic memory of water functions. Brian Josephson, the Nobel Laureate, in a letter to the New Scientist, http://www.newscientist.com/ns/971101/letters.html (expired link) says: "... advocates of homeopathic remedies attribute their effects, not to molecules present in the water, but to modifications of the water's structure. Simple-minded analysis may suggest that water, being a fluid, cannot have a structure of the kind that such a picture would demand. But cases such as that of liquid crystals, which while flowing like an ordinary fluid can maintain an ordered structure over macroscopic distances, show the limitations of such ways of thinking. There have not, to the best of my knowledge, been any refutations of homeopathy that remain valid after this particular point is taken into account. ..." According to the Encyclopaedia Britannica, "... The water molecule is not linear but bent in a special way. As a result, part of the molecule is negatively charged and part positively charged. It is thus a highly polar molecule. Hydrogen atoms in water molecules are attracted to regions of high electron density and can form weak linkages, called hydrogen bonds, with those regions. This means that the hydrogen atoms in one water molecule are attracted to the non-bonding electron pairs of the oxygen atom on an adjacent water molecule. As a result, water molecules associate strongly. In an ice crystal, the association is a highly ordered but loose structure. http://www.innerx.net/personal/tsmith/Sets2Quarks5.html When the ice melts, this orderly arrangement breaks down partially and the molecules pack more closely together. This makes the liquid denser than the solid, which is why ice forms on top of liquid water. The associative force, however, is still strong enough to prevent water molecules from separating completely even at room temperature. This continued association in the liquid state accounts for the high boiling point of water. The structure of liquid water is believed to consist of aggregates of water molecules that form and re-form continually. This short-range order, as it is called, accounts for other unusual properties of water, such as its high viscosity and surface tension. The polarity of the water molecule plays a major part in the formation of aqueous solutions...." We believe, as T. Smith, that water retains some crystalline properties, even beyond the boiling point. Apparently, due to this property of water, Jacques Benveniste, Yolene Thomas, and others claim to have established experimentally a "Memory of Water". http://www.oxytherapy.com/mailarchive/aug96/103.html (expired link). According to Keith Johnson, in physics/9807058, http://xxx.lanl.gov/abs/physics/9807058 clusters of water molecules exist optimally in certain Magic Numbers and in configurations such as Buckyball pentagonal dodecahedral structures with a closed, ideally icosahedral symmetry formed by 20 hydrogen-bonded water molecules, with their oxygen atoms at the vertices of 12 concatenated pentagons and with 10 free exterior hydrogen atoms. Coupling of these delocalized oxygen orbitals with the low-frequency cluster vibronic modes via the dynamical Jahn-Teller effect may make water buckyballs catalytic electron reservoirs and oxygenates in fuel combustion and active agents in biological systems. The broad electronic and unique low-frequency vibronic spectra of water

buckyballs may explain certain diffuse interstellar bands (DIBs) and far-infrared, ultraviolet and x-ray cosmic background radiation. D. L. Marrin http://www.zynet.co.uk/imprint/Tucson/4.htm - Water's memory notes that the tetrahedral Hydrogen bonds of water are not 'fixed' in time and space. Even in frozen water Ice, the tetrahedral bonds from Oxygen to Oxygen are each half covalent and half Hydrogen, unlike the purely covalent Carbon-Carbon tetrahedral bonds of Diamond. The tetrahedral Hydrogen water bonds are able to re-shuffle at the rate of about a trillion times per second. The manner in which this re-shuffling occurs is described by a probability function and may be represented by a random binary network, similar to that of a computer. From the perspective of cybernetics, the Hydrogen bond network in water may be considered a self-organizing system that behaves chaotically. Water molecules that are in contact with other surfaces (e.g. air) or with solutes (e.g. salts, organic molecules) arrange themselves into a variety of geometries that impart changes to the network. In this manner, water is capable of discerning 'self'' from 'non-self' and interacting with its environment. Recent findings suggest that the breaking and forming of Hydrogen bonds between macromolecules and surrounding water molecules substantially influences the 3-D structure of proteins and nucleic acids. According to Physics News Preview http://www.aip.org/physnews/preview and Physics News Update (Number 410) of the AIP, Isaacs, Shukla, Platzman, Hamann, Barbiellini, and Tulk, in the 18 January 1999 issue of Physical Review Letters, "... [study] the properties of many Comptonscattered photons ... to measure ... [the] ... ground-state electronic wavefunction [of ice] ... The ground-state wavefunction in ice indicates that there is a quantum-mechanical overlap of the electrons on neighboring H2O molecules, i.e., that the hydrogen bond is partly covalent. ... the weak hydrogen bonds between H2O molecules in ice get part of their identity from stronger covalent bonds within the H2O molecule. ... The two relatively strong electronic bonds that make up the H2O molecule itself are represented in the figure by the darker yellow clouds ... While the intermolecular bonds, or hydrogen bonds, are primarily electrostatic in nature, in which the molecules are attracted by means of separated electric charges, [they] found that the bond is in part quantum mechanical, or covalent in nature, in which electrons are spread out and shared between atoms. The quantummechanical or wavelike aspect of this bond is depicted by the lighter yellow clouds.

... Figure courtesy of Bell Labs/Lucent Technologies... Delocalization also plays an important role in determining the behavior of superconductors and other electrically conducting materials at sufficiently low temperatures. ... ".

In a March 1996 seminar held at Cranfield University in Bedford, U. K., it was determined that applications of radio frequency E/M propagations to water result in changes in the rate of formation of scaling in plumbing by "hard water". It was demonstrated that this behavioral change, resulting from application of radio frequency propagations to water, persisted for as long as five days after the water had been exposed to low frequency R.F. This observation has been attributed to the memory of water. http://www.aewt.com/tech/science.html (Also see: "Influence of Ca+ in Biological Effects of Direct and Indirect ELF Magnetic Field Stimulation" from Electro- and Magnetobiology, Journal of the International Society for Bioelectricity, Volume 20 Issue 3, 2001, ISSN: 1061-9526, http://www.bion.si/research/Ca.htm To further explain the remarkable ability of the spin field generator to transfer properties between materials, we shall invoke the experimental results of V. Poponin, which show that even the vacuum, space itself, has this property of having a memory. http://www.rialian.com/rnboyd/dnaphantom.htm V. Poponins experiments at Lebedev University in Moscow, and at the Heart-Math Institute in Arizona, have shown that the electromagnetic signature of a hermetically sealed sample of DNA will persist in a vacuum chamber for periods as long as 30 days, after the sample is removed. According to Poponin, the memory of the vacuum can be described as a localized excitation in a Fermi-Pasta-Ulam lattice. The FPU lattice is the Hamiltonian of an n-dimensional system of loosely coupled (anharmonic) oscillators. These experimental data suggest that localized excitations of DNA phantom fields are long living and can exist in non-moving and slowly propagating states. This type of behavior is distinctly different from the behavior demonstrated by other well known nonlinear localized excitations such as solitons, which are currently considered to be the best explanation of how vibrational energy propagates through the DNA. It is a remarkable and striking coincidence that a new class of localized solutions to anharmonic Fermi-Pasta-Ulam lattice (FPU), Nonlinear Localized Excitations (NLE), which have been recently obtained, demonstrate very similar dynamical features to those of the DNA phantom. Nonlinear localized excitations predicted by the FPU model also have unusually long life-times. Furthermore, they can exist in both stationary and slowly propagating forms. In Figure 3, one example of a NLE is shown which illustrates three stationary localized excitations generated by numerical simulation using the FPU model. It is worthy to note that this NLE has a surprisingly long life-time. Here, we present only one of the many possible examples of the patterns for stationary excitations which are theoretically predicted. Slowly propagating and long lived NLE are also predicted by this theory. Note that the FPU model can successfully explain the diversity and main features of the DNA phantom dynamical patterns. This model is suggested as the basis for a more general nonlinear quantum theory which may explain many of the observed subtle energy phenomena and eventually could provide a physical theory of consciousness. According to our current hypothesis, the DNA phantom effect may be interpreted as a manifestation of a new physical vacuum substructure which has been previously overlooked. It appears that this substructure can be excited from the physical vacuum in a range of energies close to zero energy provided certain specific conditions are fulfilled which are specified above. Furthermore, one can suggest that the DNA phantom effect is a specific example of a more general category of electromagnetic phantom effects. This suggests that the electromagnetic phantom effect is a more fundamental phenomenon which can be used to explain other observed phantom effects including the phantom leaf effect and the phantom limb. From this, we think that the spin field is acting as a carrier of the non-linear excitations of the vacuum, by way of the previously described species of sub-quantum particles in the interstitial spaces internal to the spin field helices. What we are saying then, is that due to a memory

mechanism similar to the description by V. Poponin of the memory of the vacuum, that the spin field is transporting the actual particles that comprise the FPU lattice, into the volume of effect the spin field, thereby transporting the memory of the vacuum which resided in that first location, into the volume and any materials which are present at the second location. Thus, we feel that the spin field is duplicating the electromagnetic 4-vector patterning, which was contained in the volume containing the alcohol, into the volume containing the water, where it should remain for some time. We intend to determine at a later date, the latency of the memory medium, which is imparted by the spin field into water. At this time, our preliminary results have shown that the memory thus imparted to the water will last for approximately 14 days. The most important application, we feel, for this remarkable property of spin field memory transfer, is in the treatment of alcohol abusers. Because, although the alcohol memory imparted into the water structure has the capacity to cause inebriation, at the same time, preliminary sample testing has shown that the water so treated does not engender any hangover. This is obvious, since we know that the hangover is a by-product of the breakdown of the alcohol by the systems of the physical body, while pure water has no such effect. Additionally, because this is just pure water, prolonged and dense consumption of spin field treated water will apparently not result in any physical damage to the body systems, such as jaundice, which can result from alcohol toxicity. There is no physical toxicity in the physical body related to ingestion of standard levels of pure water. We are concerned however, whether the toxic properties of the alcohol can be transferred in any degree, however minute, into the water, by application of the spin field. Because no hangover results from the treated water, and because the volunteers have stated that the alcohol-like exhilarations ceased in about an hour, relative to the normal eight hours which would be expected in the case of the consumption of actual alcohol, we think that there will probably be no toxicity found due to the treated water. Also, because it is just water, prolonged consumption of spin field treated water should not be expected to result in any increase in obesity. We also expect that the common symptom of desiccation in alcohol abusers will be greatly alleviated, if not eliminated, when spin field treated water is substituted for actual alcohol. We expect incidences of hospitalization due to the toxic effects of alcohol on the human physiology will be greatly reduced when this spin field derived ersatz alcohol is used to replace actual alcohol. We expect that the overall health of alcohol abusers will be substantially improved when spin field treated water replaces alcohol consumption. This regimen would then reduce the concomitant economic and emotional burdens on the State, and the families of alcohol abusers, while prolonging the life expectancy of abusers who use the water substitute. We think that it is possible that the treated water will alleviate some of the more dramatic effects of alcohol detoxification. We think that it is also possible that the treated water may eliminate or reduce alcohol dependencies, particularly physical dependencies. These two possibilities should be examined experimentally. We suggest that a series of standard clinical trials should be performed to verify these various preliminary results of consumption of spin field treated water in alcoholics and to substantiate the positive potentials for health improvements which may result by this application of the spin field in the treatment of alcoholics. We further suggest that the spin field and its potential for additional medical applications should undergo intensive experimental study. Special thanks to Tony Smith for providing many of the references on water memory.

1. R. M. Keihn "Chirality and Helicity vs. Topological Spin and Topological Torsion"
http://www22.pair.com/csdc/pd2/pd2fre52.htm

2. R. M. Keihn "Electromagnetic Waves in the Vacuum with Torsion and Spin"

http://www22.pair.com/csdc/pd2/pd2fre54.htm

3. R. M. Keihn "Spinors, Minimal Surfaces,Torsion,Helicity,Chirality,Spin, Twistors,

Orientation, Continuity, Fractals, Point Particles, Polarization, the Light Cone and the Hopf Map." http://www22.pair.com/csdc/car/carfre75.htm

4. A.A.Shpilman (sah@kaznet.kz) "Physical properties of axion (spin) fields"

http://www.pmicro.kz/MISC/UFL/Almanach/N1_98/properties.htm

5. A. A. Shpilman "Spin-field Generator"

http://www.pmicro.kz/MISC/UFL/Almanach/N3_95/S4_1a.htm

6. H. Kleinert "Theory of Fluctuating Nonholonomic Fields and Applications: Statistical

Mechanics of Vortices and Defects and New Physical Laws in Spaces with Curvature and Torsion in: Proceedings of a NATO Advanced Study Institute on Formation and Interactions of Topological Defects at the University of Cambridge, England, Plenum Press, New York, 1995" http://xxx.lanl.gov/abs/cond-mat/9503030

7. R. M. Keihn "Longitudinal, Transverse, and Torsional Waves"

http://www22.pair.com/csdc/car/carfre41.htm

8. R. M. Keihn "Links, Knots, and Braids" http://www22.pair.com/csdc/car/carfre63.htm 9. R. M. Keihn "Dynamical Phase Transitions in Fluids"
http://www22.pair.com/csdc/car/carfre43.htm

10. V. Poponin "The DNA PHANTOM EFFECT: Direct Measurement of A New Field in the
Vacuum Substructure" DNA Phantom Effect

11. J. Sarfatti "Star Gate AnholonomicTorsion Geometrodynamics Part I. The Classical Limit"
http://stardrive.org/Jack/algebra.pdf

12. J. Sarfatti "Vigier 2000 Conference" http://www.stardrive.org/vigier2000.shtml 13. Sarfatti, Corum "Anholonomic Electrodynamics" http://www.stardrive.org/Jack/corum.pdf 14. R. Coquereaux, A. Jadczyk "CONFORMAL THEORIES, CURVED PHASE SPACES,
RELATIVISTIC WAVELETS AND THE GEOMETRY OF COMPLEX DOMAINS." CPT-89/P2302, Sep 1989. 43pp. Published in Rev.Math.Phys. 2:1-44, 1990. http://www.cassiopaea.org/quantum_future/conformal_theories.htm

15. A. A. Shpilman "Excitation of "Axion (Spin) Field" in Water"

http://www.pmicro.kz/MISC/UFL/Almanach/4n99/WaterA.htm

16. A. Shipov "Torsion Field Theory" http://stardrive.org/Jack/Shipov.pdf 17. B. Page wspage@dgs.drenet.dnd.ca "Cartan's theory of forms impotent for statistical
mechanics of defects" from E-mail posted to closed list.

18. A. Frolov "Comments on Dr. Shipov's paper about torsion fields, 2001"
http://www.faraday.ru/axion.html

19. S.-P. Sirag "Torsion in Superstring Theory" http://stardrive.org/Jack/sps17.pdf

20. A. Akimov, V. Tarasenko, "Models of Polarized States of the Physical Vacuum and Torsion Fields," Sov. Phys. J., p.214, March 1992.

21. T. Smith "3-form A /\ dA - Affine Torsion"

http://www.innerx.net/personal/tsmith/topolophys.html#TorPhys

22. A. M. Mishin "The Ether Model as Result of the New Empirical Conception"
http://alexfrolov.narod.ru/mi-paper.htm

23. A. A. Shpilman [Ibid] "Physical properties of axion (spin) fields"

http://www.pmicro.kz/MISC/UFL/Almanach/N1_98/properties.htm

24. A. A. Shpilman "Effect of Axion radiation on hardness of metal"

http://www.pmicro.kz/MISC/UFL/Almanach/Exp/hardness.htm
Home Physics Spirit and Consciousness Insight Health e.e. cummings Artwork Harmony Dynamics Miscellaneous rnboyd@mip.net Penetrating

The Saykally Group

Professor Richard J. Saykally

saykally@uclink.berkeley.edu
College of Chemistry, University of California, Berkeley

Saykally Group Research Projects

Active projects include nonlinear chemical imaging nanomicroscopy(NCIN) of nanostructured materials, polymers, and biological systems, terahertz laser spectroscopy of water clusters, infrared cavity ringdown spectroscopy of ions and clusters, synchrotron X-ray spectroscopy of liquid surfaces, chemical reactions at liquid surfaces, and single photon counting IR emission spectroscopy of PAH molecules. We continue to focus on problems involving liquid water and its surface.
Updated July 28 2002 Questions/suggestions please email: knutsen@uclink4.berkeley.edu

Far Infrared Vibrational Rotational Tunnelling Spectroscopy (FIR-VRT)

This is a diagram depicting one of the two far-infrared spectrometers in our lab. Recent work has focused on Van der Waals clusters, and recent discoveries include water tetramer, pentamer, and hexamer bands.

Recent Advances in cluster detection are in part due to the introduction of the pulsed slit valve shown below. A four inch long .005" wide slit is operated in pulsed mode by driving a poppet with three General Valve solenoids at up to 50Hz. Laser light from a mid or farinfrared laser is multi-passed in front of the supersonic expansion to provide absorption pathlegnths of up to 3 meters. This source also has a detachable reservior for introcuction of non-volatile samples into the expansion by heating. The unit can be operated at up to 250C. The pulsed slit source can be applied to spectroscopic measurements at any wavelegth. Some other recent applications have been in the Cavity Ringdown Spectrometer, and for the detection of nucleotide bases in the gas phase.

This cluster source was reviewed in the litererature. Return to Saykally Group Research Interests.
Last Modified 26 September 1995 knutsen@uclink4.berkeley.edu

Cavity Ringdown Primer

The Cavity Ringdown Spectrometer is being developed in the Saykally Lab to study new molecules in molecular beams. Notable discoveries include the copper trimer, and the silicides of gold, silver, copper, and platinum, detection ao mid-infrared water clusters and amorphous ice, and expansion of the technique into the infrared for high resolution spectroscopy of gas phase biological molecules.. The Cavity Ringdown technique is depicted in this cartoon. A high intensity pulsed tunable laser intersects a supersonic molecular beam (a slit source is depicted, but we commonly utilize a pinhole source) in a highly reflective mirror cavity. The time-dependent decay of the light leaking through the mirrors is a function of the mirror reflectivity and the absorption of molecules in between them. This technique makes possible the detection of scarce quantities of novel molecular species by direct laser absorption in a molecular beam.

Water VRT Primer

Depicted in this cartoon is an example of a tunneling motion that occurs in the water trimer (a cluster of three water molecules), along with the signature spectral signal for this motion obtained by VRT (Vibrational Rotational Tunneling) laser spectroscopy, and the potential energy barrier through which the tunnelling occurs. Note that in pure water clusters, tunneling involves exchange of protons within the individual water molecules (monomers), and/or flipping of the water molecules (outside hydrogen pointing up or down) to yield a molecule with identical energy and molecular symmetry (though possiblly mirrorimage reversed). For more detailed information, visit the Far-IR Pages, or return to our Research Interests. Last Modified 31 July 2001

R.J.Saykally Group Publications

Saykally Group Cover Articles The following is a complete list of papers, in reverse order of publication, authored by The Saykally Group.

Published Papers 2002 Return to Publications Menu 270. H.-S. Kim, and R.J. Saykally, "Single Photon Infraed Emission Spectroscopy of Gaseous Polycyclic Aromatic Hydrocarbon Cations: A Direct Test for Proposed Carriers of the Unidentified Infrared Emission Bands," Astrophys. J. Supp. Series, 143, 455-467 (2002). 269.**F.N. Keutsch, David J. Wales, and R.J. Saykally, "Bifurcation tunneling dynamics in the water trimer," J. Chem. Phys. 117, 8823 (2002). **Featured in the November 1, 2002 issue of the Virtual Journal of Biological Physics Research.

268. C. Leforestier, R.S. Fellers, and R.J. Saykally, "Determination of a flexible (12D) water dimer potential via direct inversion of spectroscopic data," J. Chem. Phys. 117, 8710 (2002). 267.**K.R. Wilson, R.D. Schaller, B.S. Rude, T. Catalano, D.T. Co, J.D. Bozek, and R.J. Saykally, "Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy," J. Chem. Phys. 117, 7738-7744 (2002). **Featured by Nature in "News and Views," and by Science as "Editors' Choice." 266. R.D. Schaller, P.T. Snee, J.C. Johnson, L.F. Lee, K.R. Wilson, L.H. Haber, R.J. Saykally, T.-Q. Nguyen, and B.J. Schwartz, "Nanoscopic interchain aggregate domain formation in conjugated polymer films studied by third harmonic generation near-field scanning optical microscopy," J. Chem. Phys. 117, 6688-6698 (2002). 265. R.D. Schaller, L.F. Lee, J.C. Johnson, L.H. Haber, J. Vieceli, H. Benjamin, T.-Q. Nguyen, B.J. Schwartz, and R.J. Saykally, The Nature of Interchain Excitations in Conjugated Polymers: Spatially-Varying Solvatochromism of MEH-PPV Films Studied by Near-field Scanning Optical Microscopy (NSOM), J. Phys. Chem. B 106, 9496-9506 (2002). 264. J.C. Johnson, H.-J. Choi, K.P. Knutsen, R.D. Schaller, P. Yang, and R.J. Saykally, Single Gallium Nitride Nanowire Lasers, Nature Materials 1(2), 106-110 (2002). 263. R.D. Schaller, J. Ziegelbauer, L.F. Lee, L.H. Haber, and R.J. Saykally, "Chemically Selective Imaging of Subcellular Structure in Human Hepatocytes with Coherent Anti-Stokes Raman Scattering (CARS) Near-field Scanning Optical Microscopy (NSOM)," J. Phys. Chem. B 106, 8489-8492 (2002). 262. A.J. Huneycutt, R.J. Stickland, F. Hellberg, and R.J. Saykally, Characterization of gas-phase HC1-H2O clusters using pulsed infrared cavity ringdown spectroscopy, Proceedings of the SPIE Conferences, Photonics West 2002, Proc. SPIE Vol. 4634, p. 70-77, Methods for Ultrasensitive Detection II, Charles W. Wilkerson; Ed. (2002). 261. R.D. Schaller, J.C. Johnson, K.R. Wilson, L.F. Lee, L.H. Haber, and R.J. Saykally, Characterization of biological structures with nonlinear chemical imaging nanomicroscopy, Proceedings of the SPIE Conferences, Photonics West 2002, Proc. SPIE Vol. 4633, p. 6268, Commercial and Biomedical Applications of Ultrafast and Free-Electron Lasers, Glenn S. Edwards; Joseph Neev; Andreas Ostendorf; John C. Sutherland; Eds. (2002). 260. R.N. Casaes and R.J. Saykally, Spectroscopy (CRLAS), The McGraw-Hill 2002 Yearbook of Science & Technology, Mark D. Licker, editor, pp. 331-333 (2001). 259. P. Yang, H. Yan, S. Mao, R. Russo, J. Johnson, R. Saykally, N. Morris, J. Pham, R. He, and H.-J. Choi, Controlled growth of ZnO nanowires and their optical properties, Adv. Funct. Mater. 12, 323-331 (2002). 258.* R.D. Schaller, J.C. Johnson, K.R. Wilson, L.F. Lee, L.H. Haber, and R.J. Saykally, Nonlinear Chemical Imaging Nanomicroscopy: From Second and Third Harmonic Generation to Multiplex (Broad-bandwidth) Sum Frequency Generation Near-Field Scanning Optical Microscopy, J. Phys. Chem. B 106, 5143-5154 (2002). *Invited Cover Article. 257. J.C. Johnson, H. Yan, R.D. Schaller, P.B. Petersen, P. Yang, and R.J. Saykally, "Near-Field Imaging of Nonlinear Optical Mixing in Single Zinc Oxide Nanowires," Nano Lett. 2, 279-283 (2002). 256. N. Goldman, R.S. Fellers, M.G. Brown, L.B. Braly, C.J. Keoshian, C. Leforestier, and R.J. Saykally, Spectroscopic Determination of the Water Dimer Intermolecular Potential Energy Surface, J. Chem. Phys. 116, 10148 (2002). 255. D. Kraus, V.E. Bondybey, and R.J. Saykally, Cavity-Ringdown Spectroscopy Studies of the B2+ X2+ System of AlO, ChemPhysChem 4, 364-366 (2002). 254. R.N. Casaes, R.A. Provencal, J.B. Paul, and R.J. Saykally, High resolution pulsed infrared cavity ringdown spectroscopy: Application to laser ablated carbon clusters, J. Chem. Phys. 116, 6640-6647 (2002). 253.**K.R. Wilson, M. Cavalleri, B.S. Rude, R.D. Schaller, A. Nilsson, L.G.M. Pettersson, N. Goldman, T. Catalano, J.D. Bozek, and R.J. Saykally, Characterization of hydrogen bond acceptor molecules at the water surface using near-edge x-ray absorption finestructure spectroscopy and density functional theory, J. Phys.: Condens. Matter 14, L221-L226 (2002). **Featured by Science as Editors Choice. 2001 Return to Publications Menu 252.* **J.C. Johnson, H. Yan, R.D. Schaller, L.H. Haber, P. Yang, and R.J. Saykally, Single Nanowire Lasers, J. Phys. Chem. B 105, 11387-11390 (2001). *Cover Article. **Featured by Science as Editors Choice.

251. L.F. Lee, R.D. Schaller, L.H. Haber, and R.J. Saykally, High Spatial Resolution Imaging with Near-field Scanning Optical Microscopy in Liquids, Anal. Chem. 73, 5015 (2001). 250. F.N. Keutsch, and R.J. Saykally, Water Clusters: Untangling the mysteries of the liquid, one molecule at a time, PNAS 98, 1053310540 (2001). 249. E. Michael, C.J. Keoshian, S.K. Anderson, and R.J. Saykally, Rotational transitions in excited vibrational states of D2O, J. Mol. Spec. 208, 219-223 (2001). 248. F.N. Keutsch, N. Goldman, E.N. Karyakin, H.A. Harker, M.E.Sanz, C. Leforestier, and R.J. Saykally, Complete Characterization of the (D2O)2 Ground State: High Ka Rotation Tunneling Levels, The Royal Society of Chemistry, Faraday Discussion 118, Cluster Dynamics, University of Durham, UK, Faraday Discuss. 118, 79-93 (2001). 247. H.-S. Kim, D.R. Wagner, and R.J. Saykally, "Single Photon Infrared Emission Spectroscopy of the Gas Phase Pyrene Cation: Support for a Polycyclic Aromatic Hydrocarbon Origin of the Uidentified Infrared Emission Bands," Phys. Rev. Lett. 86, 5691 (2001). 246. F.N. Keutsch, R.S. Fellers, M.G. Brown, M.R. Viant,P.B. Petersen, and R.J. Saykally, "Hydrogen Bond Breaking Dynamics of the Water Trimer in the Translational and Librational Band Region of Liquid Water," J. Am. Chem. Soc. 123, 5938-5941 (2001). 245. **T.-Q. Nguyen, B.J. Schwartz, R.D. Schaller, J.C. Johnson, L.F. Lee, L.H. Haber, and R.J. Saykally, "Near-Field Scanning Optical Microscopy (NSOM) Studies of the Relationship Between Interchain Interactions, Morphology, Photodamage and Energy Transport in Conjugated Polymer Films," J. Phys. Chem. B 105, 5153-5160 (2001). **Featured by Science as "Editor's Choice." 244. R.J. Saykally and R. Casaes, "Cavity ringdown technique measures absorption," Laser Focus World 37, 159-162 (2001). 243. E.A. Michael, C.J. Keoshian, D.R. Wagner, S.K. Anderson, and R.J. Saykally, "Infrared Water Recombination Lasers," Chem. Phys. Lett. 338, 277-284 (2001). 242.* K.R. Wilson, B. Rude, T. Catalano, R. Schaller, J.G. Tobin, D.T. Co, and R.J. Saykally, "X-Ray Spectroscopy of Liquid Water Microjets," J. Phys. Chem. B 105, 3346-3349 (2001). *Cover Article. 241. T.F. Giesen, A.O. Van Orden, J.D. Cruzan, R.A. Provencal, R. Gendriesch, F. Lewen, G. Winnewisser, R.T. Boreiko, A.L. Betz, and R.J. Saykally, "Interstellar Detection of CCC and High Precision Laboratory Measurements near 2 THz," Astrophys. J. Lett. 551:L181-L184 (2001). 240.* T.F. Giesen, U. Berndt, K.M.T. Yamada, G. Fuchs, R. Schieder, G. Winnewisser, R.A. Provencal, F.N. Keutsch, A. Van Orden, and R.J. Saykally, "Detection of the Linear Carbon Cluster C10: Rotationally Resolved Diode Laser Spectroscopy," ChemPhysChem 4, 242-247 (2001). *Cover Article. 239. T.F. Giesen, U. Berndt, G. Fuchs, G. Winnewisser, R.A. Provencal, F.N. Keutsch, A. Van Orden, and R.J. Saykally, "IR Laser Spectroscopy of Carbon Clusters," Proceedings of the Nobel Symposium 117 on The Physics and Chemistry of Clusters, Visby, Sweden, E.E.B. Campbell and M. Larsson, editors, pp. 309-310 (2001). 238. R.J. Saykally, "Water Clusters: Building Up the Liquid One Step at a Time," Proceedings of the Nobel Symposium 117 on The Physics and Chemistry of Clusters, Visby, Sweden, E.E.B. Campbell and M. Larsson, editors, pp. 206-218 (2001). 237.* R.D. Schaller, and R.J. Saykally, "Near-field Sum Frequency Generation Imaging of CVD Zinc Selenide," Langmuir 17, 20552058 (2001). *Cover Article. 236. F.N. Keutsch, R.S. Fellers, M.R. Viant, and R.J. Saykally, "Far-IR VRT Spectroscopy of Water Clusters in the Librational Band Region of Liquid Water," J. Chem. Phys. 114, 4005-5015 (2001). 235. F.N. Keutsch, M.G. Brown, P.B. Petersen, M. Geleijns, A. van der Avoird, and R.J. Saykally, "Terahertz VRT Spectroscopy of Water Clusters in the Translational Band Region of Liquid Water," J. Chem. Phys. 114, 3994-4004 (2001). 234. F.N. Keutsch, E.N. Karyakin, A. van der Avoird, and R.J. Saykally, "The 583.2 GHz Torsional Hot-Band of (D2O)3," J. Chem. Phys. 114, 3988-3993 (2001). 233.* N. Goldman, R.S. Fellers, C. Leforestier, and R.J. Saykally, "Water Dimers in the Atmosphere: Equilibrium Constant for Water Dimerization From the VRT (ASP-W) Potential Surface," J. Phys. Chem. A 105, 515-519 (2001). *Cover Article.

2000

Return to Publications Menu 232. D.R. Wagner, H.-S. Kim, and R.J. Saykally,"Peripherally Hydrogenated Neutral Polycyclic Aromatic Hydrocarbons as Carriers of the 3 Micron Interstellar Infrared Emission Complex: Results from Single Photon Infrared Emission Spectroscopy," Astrophys. J. 545, 854-860 (2000). 231. K.R. Wilson, J.G. Tobin, A.L. Ankudinov, J.J. Rehr, and R.J. Saykally, "Extended X-Ray Absorption Fine Structure from Hydrogen Atoms in Water," Phys. Rev. Lett. 85, 4289 (2000). 230. R.D. Schaller, J.C. Johnson, and R.J. Saykally, "Nonlinear Chemical Imaging Microscopy: Near-Field Third Harmonic Generation Imaging of Human Red Blood Cells," Analytical Chemistry 72, 5361-5364 (2000). 229. D.R. Wagner, and R.J. Saykally, "Ringing the changes," Chemistry in Britain 36, 47-49 (2000). 228. L.B. Braly, K. Liu, M.G. Brown, F.N. Keutsch, R.S. Fellers, and R.J. Saykally, "Terahertz Laser Spectroscopy of the Water Dimer Intermolecular Vibrations. II. (H2O)2," J. Chem. Phys. 112, 10314 (2000). 227. L.B. Braly, J.D. Cruzan, K. Liu, R.S. Fellers, and R.J. Saykally, "Terahertz Laser Spectroscopy of the Water Dimer Intermolecular Vibrations. I. (D2O)2," J. Chem. Phys. 112, 10293 (2000). 226.* R.D. Schaller, C. Roth, D.H. Raulet, and R.J. Saykally, "Near-field Second Harmonic Imaging of Granular Membrane Structures in Natural Killer Cells," J. Phys. Chem. B 104, 5217 (2000). *Cover Article. 225. R.A. Provencal, K. Roth, J.B. Paul, C.N. Chapo, R.N. Casaes, R.J. Saykally, G.S. Tschumper, and H.F. Schaefer, III, "Hydrogen Bonding in Alcohol Clusters: A Comparative Study by Infrared Cavity Ringdown Laser Absorption Spectroscopy," J. Phys. Chem. A 104,1423 (2000).

1999 Return to Publications Menu 224. M.G. Brown, F.N. Keutsch, L.B. Braly, and R.J. Saykally, "High Symmetry Effects on Hydrogen Bond Rearrangement: The 4.1 THz Vibrational Band of (D2O)4," J. Chem. Phys. 111, 7801 (1999). 223. M.G. Brown, M.R. Viant, R.P. McLaughlin, C.J. Keoshian, E. Michael, J.D. Cruzan, R.J.-Saykally, and A. van der Avoird, "Quantitative Characterization of the Water Trimer Torsional Manifold by Terahertz Laser Spectroscopy and Theoretical Analysis. II. (H2O)3," J. Chem. Phys. 111, 7789 (1999). 222. D. Kraus, R.J. Saykally, and V.E. Bondybey, "Cavity ringdown spectroscopy search for transition metal dimers," Chemical Physics 247, 431-434 (1999). 221. A. OKeefe, J.J. Scherer, J.B. Paul, and R.J. Saykally, "Cavity-Ringdown Laser Spectroscopy: History, Development, and Applications," 1997 ACS Symposium Series 720 on Cavity-ringdown spectroscopy: an ultratrace-absorption measurement technique, Kenneth W. and Marianna A. Busch, editors, pp. 71-92 (1999). 220.* R.A. Provencal, J.B. Paul, C.N. Chapo, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy," Spectroscopy 14, 24 (1999). *Cover Article. 219. E.N. Karaykin, G.T. Fraser, J.G. Loeser, and R.J. Saykally, "Rotation-Tunneling Spectrum of the Deuterated Ammonia Dimer," J. Chem. Phys 110, 9555 (1999). 218. D. Kraus, R.J. Saykally, and V.E. Bondybey, "Cavity Ringdown Laser Absorption Spectra of Tungsten Oxide," Chem. Phys. Lett. 295, 285-288 (1998). 217. R.A. Provencal, J.B. Paul, K. Roth, C. Chapo, R.N. Casaes, R.J. Saykally, G.S. Tschumper, and H.F. Schaefer, III, "Infrared cavity ringdown spectroscopy of methanol clusters: Single donor hydrogen bonding," J. Chem. Phys. 110, 4258 (1999). 216. R.S. Fellers, L.B. Braly, C. Leforestier, and R.J. Saykally, "Fully Coupled Six Dimensional Calculations of the Water Dimer Vibration-Rotation-Tunneling States with Split Wigner Pseudospectral Method II: Improvements and Tests of Additional Potentials," J. Chem. Phys. 110, 6306 (1999). 215. M.R. Viant, M.G. Brown, J.D. Cruzan, M. Geleijns, A. van der Avoird, and R.J. Saykally, "Quantitative Characterization of the (D2O)3 Torsional Manifold by Terahertz Laser Spectroscopy and Theoretical Analysis," J. Chem. Phys. 110, 4369 (1999).

214. C.J. Chapo, J.B. Paul, R.A. Provencal, K. Roth, and R.J. Saykally, "Is Arginine Zwitterionic or Neutral in the Gas-Phase? Results from IR Cavity Ringdown Spectroscopy," J. Am. Chem. Soc. 120, 12956-12957 (1998). 213. J.B. Paul, R.A. Provencal, C. Chapo, K. Roth, R. Casaes, and R.J. Saykally, "Infrared Cavity Ringdown Spectroscopy of the Water Cluster Bending Vibrations," J. Phys. Chem. A 103, 2972 (1999). 212. S. Henrichs, C.P. Collier, R.J. Saykally, Y.R. Shen and J.R. Heath, "The Dielectric Function of Silver Nanoparticle Langmuir Monolayers Compressed Through the Metal Insulator Transition," J. Am. Chem. Soc. 122, 4077-4083 (2000). 211. R.S. Fellers, C. Leforestier, L.B. Braly, M.G. Brown, and R.J. Saykally, "Spectroscopic Determination of the Water Pair Potential," Science 284, 945 (1999).

1998 Return to Publications Menu 210. M.G. Brown, F.N. Keutsch, and R.J. Saykally, "The Bifurcation Rearrangement in Cyclic Water Clusters: Breaking and Making Hydrogen Bonds," J. Chem. Phys. 109, 9645 (1998). 209. J.B. Paul, R.A. Provencal, C. Chapo, A. Pettersson, and R.J. Saykally, "Infrared Cavity Ringdown Spectroscopy of Water Clusters: O-D Stretching Bands," J. Chem. Phys. 109, 10201 (1998). 208. R.A. Provencal, J.B. Paul, E. Michael, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy," Photonics Spectra 32, 159-166 (1998). 207. J.D. Cruzan, M.R. Viant, M.G. Brown, D.D. Lucas, K. Liu, and R.J. Saykally, "Terahertz laser VRT spectrum of the water pentamer-d10: Constraints on the bifurcation tunneling dynamics," Chem. Phys. Lett. 292, 667-676 (1998). 206. J.B. Paul, R.A. Provencal, and R.J. Saykally, "Characterization of the (D2O)2 Hydrogen Bond-Acceptor Antisymmetric Stretch by IR-Cavity Ringdown Laser Absorption Spectroscopy," J. Phys. Chem. A 102, 3279 (1998). 205. R.J. Saykally, "Water Clusters," in The 1999 McGraw-Hill Yearbook of Science & Technology, Sybil P. Parker, editor, pp. 397-399 (1998). 204.* J.B. Paul, R.A. Provencal, C. Chapo, E. Michael, A. Pettersson, and R.J. Saykally, "Infrared Cavity Ringdown Laser Absorption Spectroscopy of Transient Species in Pulsed Supersonic Expansions," 1997 ACS Symposium Series on Cavity-Ringdown Spectroscopy: an ultratrace-absorption measurement technique, Kenneth W. and Marianna A. Busch, editors, pp. 162-173 (1999). *Cover article. 203. J.J. Shiang, J.R. Heath, C.P. Collier, and R.J. Saykally, "Cooperative Phenomena in Artificial Solids Made from Silver Quantum Dots: The Importance of Classical Coupling," J. Phys. Chem. B 102, 3425 (1998). 202.* S.E. Henrichs, J.L. Sample, J.J. Shiang, J.R. Heath, C.P. Collier, and R.J. Saykally, "High Contrast Read/Write Optical Data Storage Using Silver Quantum Dot Monolayers," Nature (1999). *Cover article. 201. M.G. Brown, M.R. Viant, and R.J. Saykally, "Far Infrared Laser VRT Spectroscopy of Water Clusters," Proceedings of the 1997 NATO-Advanced Study Institute Conference on Recent Theoretical and Experimental Advances in Hydrogen Bonded Clusters, Heraklion, Crete, Greece, S.S. Xantheas, editors, pp. 101-108 (2000). 200.* A. Van Orden and R.J. Saykally, "Small Carbon Clusters: Spectroscopy, Structure, and Energetics," Chemical Reviews 98, 6, 23132357 (1998). *Cover article. 199. D.J. Cook, S. Schlemmer, N. Balucani, D.R. Wagner, J.A. Harrison, B. Steiner, and R.J. Saykally, "Single Photon Infrared Emission Spectroscopy: A Study of IR Emission from UV Laser Excited PAHs between 3 and 15 m," J. Phys. Chem. A 102, 1465 (1998). 198. D.J. Cook and R.J. Saykally, "Simulated Infrared Emission Spectra of Highly Excited Polyatomic Molecules: A detailed model of the PAH-UIR hypothesis," Astrophys. J. 493, 793-802 (1998).

1997 Return to Publications Menu

197. C.P. Collier, R.J. Saykally, J.J. Shiang, S.E. Henrichs, and J.R. Heath, "Reversible Tuning of Silver Quantum Dot Monolayers Through the Metal-Insulator Transition," Science 277, 1978 (1997). 196. A.I. Boldyrev, J. Simons, J.J. Scherer, J.B. Paul, C.P. Collier, and R.J. Saykally, "On the ground electronic states of copper silicide and its ions," J. Chem. Phys. 108, 5728 (1998). 195. M.R. Viant, J.D. Cruzan, D.D. Lucas, M.G. Brown, K. Liu, and R.J. Saykally, "Pseudorotation In Water Trimer Isotopomers Using Terahertz Laser Spectroscopy," J. Phys. Chem. A 101, 9032 (1997). 194. J.D. Cruzan, M.R. Viant, M.G. Brown and R.J. Saykally, "Terahertz Laser Vibration-Rotation-Tunneling Spectroscopy of the Water Tetramer," J. Phys. Chem. A 101, 9022 (1997). 193. K. Liu, M.G. Brown, J.D. Cruzan, and R.J. Saykally, "Terahertz Laser Spectroscopy of the Water Pentamer: Structure and Hydrogen Bond Rearrangement Dynamics," J. Phys. Chem. A 101, 9011 (1997). 192.* K. Liu, M.G. Brown, and R.J. Saykally, "Terahertz Laser Vibration-Rotation-Tunneling Spectroscopy and Dipole Moment of a Cage Form of the Water Hexamer," J. Phys. Chem. A 101, 8995 (1997). *Cover article. 191.* J.B. Paul, J.J. Scherer, A. O'Keefe, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy," Laser Focus World 33, 71-80 (1997). *Cover article. 190.* J.B. Paul and R.J. Saykally, "Cavity Ringdown Laser Spectroscopy Absorption," Analytical Chemistry A 69, 287 (1997). *Cover article. 189. J.B. Paul, C.P. Collier, J.J. Scherer, A. O'Keefe, and R.J. Saykally, "Direct Measurement of Water Cluster Concentrations by Infrared Cavity Ringdown Laser Absorption Spectroscopy," J. Phys. Chem. A 101, 5211 (1997). 188. J.R. Heath and R.J. Saykally, "Space Carbon: Neutral Pathways?," Science 274, 1480 (1996). 187. J.K. Gregory, D.C. Clary, K. Liu, M.G. Brown, and R.J. Saykally, "The Water Dipole Moment in Condensed Phases: Insights Through Cluster Studies," Science 275, 814 (1997). 186. C. Leforestier, L.B. Braly, K. Liu, M.J. Elrod, and R.J. Saykally, "Fully Coupled 6D Calculations of the Water Dimer VRT States with a Split Wigner Pseudo-Spectral Approach," J. Chem. Phys. 106, 8527 (1997).

1995 - 1996 Return to Publications Menu 185. A. Van Orden, R.A. Provencal, F.N. Keutsch, and R.J. Saykally, "Infrared Laser Spectroscopy of Jet-Cooled Carbon Clusters: The [nu]5 Band of Linear C9," J. Chem. Phys. 105, 6111 (1996). 184. J.D. Cruzan, M.G. Brown, K. Liu, L.B. Braly, and R.J. Saykally, "The far-infrared vibration-rotation-tunneling spectrum of the water tetramer-d8," J. Chem. Phys. 105, 6634 (1996). 183. E.H.T. Olthof, A. van der Avoird, P.E.S. Wormer, K. Liu, and R.J. Saykally, "Tunneling dynamics, symmetry, and far-infrared spectrum of the rotating water trimer, II. Calculations and experiments," J. Chem. Phys. 105, 8051 (1996). 182. K. Liu, J.K. Gregory, M.G. Brown, C. Carter, R.J. Saykally, and D.C. Clary, "Characterization of A Cage Form of The Water Hexamer," Nature 381 , 501 (1996). 181.* J.J. Scherer, D.J. Rakestraw, A. O'Keefe, J.B. Paul, C.P. Collier, and R.J. Saykally, "Cavity Ringdown Laser Spectroscopy: A New Ultrasensitive Absorption Technique," Spectroscopy 11 , 46-50 (1996). *Cover article. 180. K. Liu, M.G. Brown, and R.J. Saykally, "Far-Infrared VRT Spectroscopy of Two Water Trimer Isotopomers: Vibrationally Averaged Structures and Rearrangement Dynamics," Molecular Physics 89, 1373 (1996). 179.* K. Liu, J.D. Cruzan, and R.J. Saykally, "Water Clusters," Science 271 , 929 (1996) - Invited Article. *Cover article. 178. K. Liu, R.S. Fellers, M.R. Viant, R.P. McLaughlin, M.G. Brown, and R.J. Saykally, "A Long Path Length Pulsed Slit Valve Appropriate for High Temperature Operation: Infrared Spectroscopy of Jet-cooled Large Water Clusters and Nucleotide Bases" Rev. Sci. Instrum. 67 , 410 (1996).

177. A. Van Orden and R.J. Saykally, "Carbon," in The 1997 McGraw-Hill Yearbook of Science & Technology, Sybil P. Parker, editor, pp. 71-73 (McGraw-Hill, Inc. 1996). 176. K. Liu, M.G. Brown, J.D. Cruzan, and R.J. Saykally, "VRT Spectra of the Water Pentamer: Structure and Dynamics," Science 271 , 62 (1996). 175. M.R. Viant, R.S. Fellers, R.P. McLaughlin, and R.J. Saykally, "Infrared Laser Spectroscopy of Uracil in a Pulsed Slit Source," J. Chem. Phys. 103 , 9502 (1995). 174. J.J. Scherer, D. Voelkel, D.J. Rakestraw, J.B. Paul, C.P. Collier, A. O'Keefe, and R.J. Saykally, "Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS)," Chem. Phys. Lett. 245 , 273-280 (1995). 173. J.B. Paul, C.P. Collier, J.J. Scherer, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy and Time-of-Flight Mass Spectroscopy of Jet-cooled Platinum Silicides," J. Chem. Phys. 104 , 2782 (1996). 172. J.D. Cruzan, L.B. Braly, K. Liu, J.G. Loeser, M.G. Brown, and R.J. Saykally, "Quantifying Hydrogen Bond Cooperativity in Water: VRT Spectroscopy of the Water Tetramer," Science 271 , 59 (1996). 171. J.J. Scherer, J.B. Paul, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy of the Jet-cooled Aluminum Dimer," Chem. Phys. Lett. 242 , 395-400 (1995). 170. D.J. Cook, S. Schlemmer, N. Balucani, D.R. Wagner, B. Steiner, and R.J. Saykally, "Infrared emission spectra of candidate interstellar aromatic molecules," Nature 380 , 227 (1996). 169. J.J. Scherer, J.B. Paul, C.P. Collier, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy (CRLAS) and Time-ofFlight Mass Spectroscopy of Jet-cooled Gold Silicides," J. Chem. Phys. 103 , 9187 (1995). 168. J.J. Scherer, J.B. Paul, C.P. Collier, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy (CRLAS) and Time-ofFlight Mass Spectroscopy of Jet-cooled Silver Silicides," J. Chem. Phys. 103 , 113 (1995). 167. A. Van Orden, R.A. Provencal, T.F. Giesen, and R.J. Saykally, "Characterization of Silicon-Carbon Clusters by Infrared Laser Spectroscopy: The [nu]1 Band of SiC4," Chem. Phys. Lett. 237 , 77-80 (1995). 166. J.J. Scherer, J.B. Paul, C.P. Collier, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy and Time-of-Flight Mass Spectroscopy of Jet-cooled Copper Silicides," J. Chem. Phys. 102 , 5190 (1995). 165. A. Van Orden, J.D. Cruzan, R.A. Provencal, T.F. Giesen, R.T. Boreiko, A.L. Betz, and R.J. Saykally, "A Search for the C3 Carbon Cluster in the Interstellar Medium," Proceedings of the 1994 Kuiper Airborne Astronomy Symposium, NASA-Ames Research Center, Moffett Field, CA, Astron. Soc. Pac. Conf. Ser., 73, 67-70 (1995). 164. M.J. Elrod and R.J. Saykally, "Determination of the Intermolecular Potential Energy Surface for (HCl)2 from VRT Spectra," J. Chem. Phys. 103 , 933 (1995). 163. M.J. Elrod and R.J. Saykally, "Vibration-Rotation-Tunneling Dynamics Calculations for the Four Dimensional (HCl)2 System: A Test of Approximate Models," J. Chem. Phys. 103 , 921 (1995).

1994 Return to Publications Menu 162. E.H.T. Olthof, A. van der Avoird, P.E.S. Wormer, J.G. Loeser, and R.J. Saykally, "The Nature of Monomer Inversion in the Ammonia Dimer," J. Chem. Phys. 101 , 8443 (1994). 161. A. Van Orden, T.F. Giesen, R.A. Provencal, H.J. Hwang, and R.J. Saykally, "Characterization of Silicon-Carbon Clusters by Infrared Laser Spectroscopy: The [nu]3([sigma]u) Band of Linear Si2C3," J. Chem. Phys. 101 , 10237 (1994). 160. G.C.M. van der Sanden, P.E.S. Wormer, A. van der Avoird, C.A. Schmuttenmaer, and R.J. Saykally, "Close coupling results for inelastic collisions of NH3 and Ar: A stringent test of a spectroscopic potential," Chem. Phys. Lett. 226 , 22-26 (1994). 159. S. Schlemmer, D.J. Cook, J.A. Harrison, B. Wurfel, W. Chapman, and R.J. Saykally, "Are PAH Molecules Responsible for the Unidentified Interstellar Infrared Bands?," Science 265 , 1686 (1994). 158. T.F. Giesen, A. Van Orden, H.J. Hwang, R.S. Fellers, R.A. Provencal, and R.J. Saykally, "Infrared Laser Spectroscopy of the Linear C13 Carbon Cluster," Science 265 , 756 (1994).

157. K. Liu, M.J. Elrod, J.G. Loeser, J.D. Cruzan, N. Pugliano, J.A. Rzepiela, M. Brown, and R.J. Saykally, "FIRVRTS of The Water Trimer," Faraday Division, The Royal Society of Chemistry, Discussion No. 97, "Structure and Dynamics of van der Waals Complexes," Durham, U.K., Faraday Discuss. 97 , 35-41 (1994). 156.* M.J. Elrod and R.J. Saykally, "Many-body Effects in Intermolecular Forces," in van der Waals Clusters II , a special thematic issue of Chemical Reviews, J. Michl, Editor, 94 , 7, 1975-1997 (1994). *Cover article. 155.* J.J. Scherer, J.B. Paul, A. O'Keefe, and R.J. Saykally, "Cavity Ringdown Laser Absorption Spectroscopy: History, Development, and Application to Pulsed Molecular Beams," Chemical Reviews 97, 1, 25-51 (1997). *Cover article. 154. C.A. Schmuttenmaer, R.C. Cohen, and R.J. Saykally, "Spectroscopic Determination of the Intermolecular Potential Energy Surface for Ar-NH3," J. Chem. Phys. 101 , 146 (1994). 153. C.A. Schmuttenmaer, J.G. Loeser, and R.J. Saykally, "Vibration-Rotation-Tunneling Spectroscopy of Ar-NH3," J. Chem. Phys. 101 , 139 (1994). 152. K. Liu, J.G. Loeser, M.J. Elrod, B.C. Host, J.A. Rzepiela, and R.J. Saykally, "Dynamics of Structural Rearrangements in the Water Trimer," J. Am. Chem. Soc. 116 , 3507-3512 (1994). 151. J.J. Scherer, J.B. Paul, A. O'Keefe, and R.J. Saykally, "CRLAS: A New Analytical Technique for Cluster Science," in Advances in Metal and Semiconductor Cluster, Volume 3 , M.A. Duncan, editor, pp. 149-180 (JAI Press Inc. 1995). 150. M.J. Elrod, R.J. Saykally, A.R. Cooper, and J.M. Hutson, "Non-additive intermolecular forces from the spectroscopy of Van der Waals trimers: far-infrared spectra and calculations on Ar2-DC1," Molecular Physics 81 , 579-598 (1994). 149. Richard J. Saykally, "Tunable Far Infrared Laser Spectroscopy of Clusters," Proceedings of the 1993 Eleventh International Conference on Laser Spectroscopy, Hot Springs, Virginia, editors: L. Bloomfield, T. Gallagher, and D. Larson, AIP Press, Conference Proceedings No. 290 , pp. 139-143 (1994). 148. L. Dore, R.C. Cohen, C.A. Schmuttenmaer, K.L. Busarow, M.J. Elrod, J.G. Loeser, and R.J. Saykally, "Far Infrared VibrationRotation-Tunneling Spectroscopy and the Intermolecular Potential of Methane-Water: A Prototypical Hydrophobic System," J. Chem. Phys. 100 , 863 (1994).

1993 Return to Publications Menu 147. D.W. Steyert, M.J. Elrod, and R.J. Saykally, "Far-Infrared Laser Vibration-Rotation- Tunneling Spectroscopy of the Propane-Water Complex: Torsional Dynamics of the Hydrogen Bond," J. Chem. Phys. 99 , 7431 (1993). 146. D.W. Steyert, M.J. Elrod, R.J. Saykally, F.J. Lovas, and R.D. Suenram, "The Fourier Transform Microwave Spectrum of the Propane-Water Complex: A Prototypical Water- Hydrophobe System," J. Chem. Phys. 99 , 7424 (1993). 145. A.L. Cooksy, M.J. Elrod, R.J. Saykally, and W. Klemperer, "Dipole Moment Analysis of Excited Van der Waals Vibrational States of ArH35Cl," J. Chem. Phys. 99 , 3200 (1993). 144. A. Van Orden, H.J. Hwang, E.W. Kuo, and R.J. Saykally, "Infrared Laser Spectroscopy of Jet-Cooled Carbon Clusters: The Bending Dynamics of Linear C9," J. Chem. Phys. 98 , 6678 (1993). 143. R.J. Saykally and G.A. Blake, "Molecular Interactions and Hydrogen Bond Tunneling Dynamics: Some New Perspectives," Science 259 , 1570 (1993) - Invited Article. 142. H.J. Hwang, A. Van Orden, K. Tanaka, E.W. Kuo, J.R. Heath, and R.J. Saykally, "Infrared laser spectroscopy of jet-cooled carbon clusters: The structure of triplet C6," Molecular Physics 79 , 769-776 (1993). 141. M.J. Elrod, J.G. Loeser, and R.J. Saykally, "An Investigation of Three-body Effects in Intermolecular Forces III. Far Infrared Laser Vibration-Rotation-Tunneling Spectroscopy of the Lowest Internal Rotor States of Ar2HC1," J. Chem. Phys. 98 , 5352 (1993). 140. H.J. Hwang, A.K. Van Orden, K. Tanaka, E.W. Kuo, J.R. Heath, and R.J. Saykally, "Infrared Laser Spectroscopy of Jet-Cooled Carbon Clusters: The Structure and Spectroscopy of 3[Sigma] C6," Proceedings of the 1993 Opt ical Society of America/High Resolution Spectroscopy, Salt Lake City, Utah. 139. R.J. Saykally, "Detecting Pure Carbon Clusters in the ISM," Proceedings of the 1992 Conference on Astronomical Infrared Spectroscopy: Future Observational Directions, Calgary, Alberta, Canada, Sun Kwok (ed.), ASP Conference Series, Vol. 41 , 1993.

138. J.R. Heath, A.Van Orden, H.J. Hwang, E.W. Kuo, K. Tanaka, and R.J. Saykally, "Toward the Detection of Pure Carbon Clusters in the ISM," Proceedings of the Topical Meeting of the COSPAR Interdisciplinary Scientific Commission F (Meeting F3) of the COSPAR Twenty-ninth Plenary Meeting held in Washington, DC, U.S.A. 28 August-5 September, 1992, Adv. Space Res. Vol. 15 , No.3, pp. (3)25(3)33, 1995. 137. N. Pugliano, J.D. Cruzanys. 98 , 6600 (1993). 136. **R.C. Cohen and R.J. Saykally, "Determination of an Improved Intermolecular Global Potential Energy Surface for Ar-H2O from Vibration-Rotation-Tunneling Spectroscopy," J. Chem. Phys. 98 , 6007 (1993). **Selected as one of top ten papers in "What's Hot in chemistry..." by Current Contents, 1995. 135. N. Pugliano and R.J. Saykally, "The Measurement of Quantum Tunneling Between Chiral Isomers of the Water Trimer," Science 257 , 1937 (1992). 134. M.J. Elrod, B.C. Host, D.W. Steyert, and R.J. Saykally, "Far Infrared Vibration- Rotation-Tunneling Spectroscopy of ArDCl: A Critical Test of the H6(4,3,0) Potential Surface," Molecular Physics 79 , 245-251 (1993).

1992 Return to Publications Menu 133. J.W.I. van Bladel, A. van der Avoird, P.E.S. Wormer, and R.J. Saykally, "Computational Exploration of the Six-Dimensional Vibration-Rotation-Tunneling Dynamics of (NH3)2," J. Chem. Phys. 97 , 4750 (1992). 132. J.G. Loeser, C.A. Schmuttenmaer, R.C. Cohen, M.J. Elrod, D.W. Steyert, R.J. Saykally, R.E. Bumgarner, and G.A. Blake, "Multidimenional Hydrogen Tunneling Dynamics in the Ground Vibrational State of the Ammonia Dimer," J. Chem. Phys. 97 , 4727 (1992). 131. N. Pugliano and R.J. Saykally, "Measurement of the [nu]8 Intermolecular Vibration of (D2O)2 by Tunable Far Infrared Laser Spectroscopy," J. Chem. Phys. 96 , 1832 (1992). 130. R.C. Cohen and R.J. Saykally, "Vibration-Rotation-Tunneling Spectroscopy of the van der Waals Bond: A New Look at Intermolecular Forces," J. Phys. Chem. 96 , 1024 (1992) - Invited Article.

1991 Return to Publications Menu 129. R.C. Cohen and R.J. Saykally, "Multidimensional Intermolecular Dynamics from Tunable Far Infrared Laser Spectroscopy: Angular-Radial Coupling in the Intermolecular Potential of Argon-H2O," J. Chem. Phys. 95 , 7891 (1991). 128. J.R. Heath and R.J. Saykally, "Probing the Structures and Vibrational Dynamics of Carbon Clusters," in On Clusters and Clustering: From Atoms to Fractals , P.J. Reynolds, editor, pp. 7-21 (Elsevier Science Publishers B.V. 1993). 127. J.R. Heath, A. Van Orden, E. Kuo, and R.J. Saykally, "The [nu]5 Band of C7," Chem. Phys. Lett. 182 , 17 (1991). 126. M.J. Elrod, D.W. Steyert, and R.J. Saykally, "An Investigation of Three-Body Effects in Intermolecular Forces. II. Far Infrared Vibration-Rotation-Tunneling Laser Spectroscopy of Ar2HC1," J. Chem. Phys. 95 , 3182 (1991). 125. J.R. Heath, J.M. Hawkins, P.A. Alivasatos, R.J. Saykally, T.A. Lewis, S.D. Loren, A. Meyer, Y. Shibato, S. Tolbert, and J. Shang, "C60 Research at the University of California at Berkeley," Proceedings of the 1990 Materials Research Science Conference, Boston, MA. 124. C.A. Schmuttenmaer, R.C. Cohen, J.G. Loeser, and R.J. Saykally, "Far-Infrared Vibration-Rotation-Tunneling Spectroscopy of ArNH3: Intermolecular Vibrations and Effective Angular Potential Energy Surface," J. Chem. Phys. 95 , 9 (1991). 123. R.C. Cohen and R.J. Saykally, "Multidimensional Intermolecular Potential Surfaces from Vibration-Rotation-Tunneling (VRT) Spectra of van der Waals Complexes," Ann. Rev. Phys. Chem. 42 , 369 (1991). 122. J.M. Hawkins, T.A. Lewis, S.D. Loren, A. Meyer, J.R. Heath, R.J. Saykally, and F.J. Hollander, "A Crystallographic Analysis of C60 (Buckminsterfullerene)," J. Chem. Soc., Chem. Commun. 775 (1991). 121. G.A. Blake, K.B. Laughlin, R.C. Cohen, K.L. Busarow, D.-H. Gwo, C.A. Schmuttenmaer, D.W. Steyert, and R.J. Saykally, "The Berkeley Tunable Far Infrared Laser Spectrometers," Rev. Sci. Inst. 62, 1701 (1991).

120. G.A. Blake, K.B. Laughlin, R.C. Cohen, K.L. Busarow, D.-H. Gwo, C.A. Schmuttenmaer, D.W. Steyert, and R.J. Saykally, "Tunable Far Infrared Laser Spectrometers," Rev. Sci. Inst. 62, 1693 (1991) - Invited Review. 119. B.E. Wurfel, N. Pugliano, S.E. Bradforth, R.J. Saykally, and G.C. Pimentel, "Broadband Transient Infrared Laser Spectroscopy of Trifluorovinyl Radical - C2F3*; Experimental and Ab Initio Results," J. Phys. Chem. 95 , 2932 (1991). 118. M. Havenith, R.C. Cohen, K.L. Busarow, D.-H. Gwo, Y.T. Lee, and R.J. Saykally, "Measurement of the Intermolecular VibrationRotation-Tunneling (VRT) Spectrum of the Ammonia Dimer by Tunable Far Infrared Laser Spectroscopy," J. Chem. Phys. 94, 4776 (1991). 117. J.R. Heath and R.J. Saykally, "The Structure of the C4 Cluster Radical," J. Chem. Phys. 94, 3271 (1991). 116. J.R. Heath and R.J. Saykally, "Infrared Laser Absorption Spectroscopy of the [nu]4 ([sigma]u) Fundamental and Associated [nu]11 ([pi]u) Hot Band of C7: Evidence for Alternating Rigidity in Linear Carbon clusters," J. Chem. Phys. 94, 1724 (1991). 115. M.J. Elrod, D.W. Steyert, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of a Ternary van der Waals Cluster Ar2HCl: A Sensitive Probe of Three-Body Forces," J. Chem. Phys. 94 , 58 (1991).

1990 Return to Publications Menu 114. J.M. Hawkins, T.A. Lewis, S.D. Loren, A. Meyer, J.R. Heath, Y. Shibato, and R.J. Saykally, "Organic Chemistry of C60 (Buckminsterfullerene): Chromatography and Osmylation," J. Org. Chem. 55 , 6250 (1990). 113. D.-H. Gwo, M. Havenith, K.L. Busarow, R.C. Cohen, C.A. Schmuttenmaer, and R.J. Saykally, "Tunable Far-IR Laser Spectroscopy of van der Waals Bonds: The jkc = 10<-00 S Bending Vibration of Ar-14NH3," Molec. Phys. 71, 453 (1990). 112. J.R. Heath and R.J. Saykally, "The C9 Cluster: Structure and Infrared Frequencies," J. Chem. Phys. 93, 8392 (1990). 111. R.C. Cohen and R.J. Saykally, "Extending the Collocation Method to Multidimensional Molecular Dynamics: Direct Determination of the Intermolecular Potential of Ar-H2O from Tunable Far Infrared Laser Spectroscopy," J. Phys. Chem. 94, 7991 (1990). 110. C.A. Schmuttenmaer, R.C. Cohen, N. Pugliano, J.R. Heath, A.L. Cooksy, K.L. Busarow, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of Jet-Cooled Carbon Clusters: The n2 Bending Vibration of C3," Science 249, 897 (1990). 109. J.R. Heath, R.A. Sheeks, A.L. Cooksy, and R.J. Saykally, "The C7 Cluster: Structure and Infrared Frequencies," Science 249, 895 (1990). 108. A. O'Keefe, J.J. Scherer, A.L. Cooksy, R. Sheeks, J.R. Heath, and R.J. Saykally, "Cavity Ring Down Dye Laser Spectroscopy of Jet Cooled Metal Clusters: Cu2 and Cu3," Chem. Phys. Lett. 172, 214 (1990). 107. E.R. Keim, M.L. Polak, J.C. Owrutsky, J.V. Coe, and R.J. Saykally, "Absolute Infrared Vibrational Band Intensities of Molecular Ions Determined by Direct Laser Absorption Spectroscopy in Fast Ion Beams," J. Chem. Phys. 93, 3111 (1990). 106. H. Petek, D.J. Nesbitt, J.C. Owrutsky, C.S. Gudeman, X. Yang, D.O. Harris, C.B. Moore, and R.J. Saykally, "A Study of the Structure and Dynamics of the Hydronium Ion by High Resolution Infrared Laser Spectroscopy. III. The n3 Band of D3O+," J. Chem. Phys. 92, 3257 (1990). 105. R.C. Cohen, K.L. Busarow, Y.T. Lee, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of van der Waals Bonds: The Intermolecular Stretching Vibration and Effective Radial Potentials for Ar-H2O," J. Chem. Phys. 92, 169 (1990). LBL-27537

1989 Return to Publications Menu 104. R.C. Cohen, K.L. Busarow, C.A. Schmuttenmaer, Y.T. Lee, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of Ultracold Free Radicals," Chem. Phys. Lett. 164 , 321 (1989). LBL-27939 103. D.C. Hovde, E.R.Keim, and R.J. Saykally, "Velocity Modulation Laser Spectroscopy of Molecular Ions: The Hyperfine-Resolved Rovibrational Spectrum of HF+," Mol. Phys. 68 , 599 (1989). 102. J.C. Owrtusky, E.R. Keim, J.V. Coe, and R.J. Saykally, "Absolute IR Intensities of the [nu]3 Bands of HN2+ and HCO+ Determined by Direct Laser Absorption Spectroscopy in Fast Ion Beams, " J. Phys. Chem. 93 , 5960 (1989).

101. R.J. Saykally, "Far-Infrared Laser Spectroscopy of van der Waals Bonds: A New Probe of Intermolecular Forces," Accts. Chem. Res. 22 , 295 (1989). LBL-26553 100. J.R. Heath, A.L. Cooksy, M.H.W. Gruebele, C.A. Schmuttenmaer, and R.J. Saykally, "Diode Laser Absorption Spectroscopy of Supersonic Carbon Cluster Beams: The [nu]3 Spectrum of C5," Science 244 , 564 (1989). 99. M. Polak, M.H.W. Gruebele, B.W. DeKock, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Molecular Ions: The [nu]4 Band of Ammonium, Molec. Phys. 66 , 1193 (1989). 98. K.L. Busarow, R.C. Cohen, G.A. Blake, K.B. Laughlin, Y.T. Lee, and R.J. Saykally, "Measurement of the Perpendicular RotationTunneling Spectrum of the Water Dimer by Tunable Far Infrared Laser Spectroscopy in a Planar Supersonic Jet," J. Chem. Phys. 90, 3937 (1989). LBL-26174 97. J.V. Coe, J.C. Owrutsky, E.R. Keim, N.V. Agman, D.C. Hovde, and R.J. Saykally, "Sub-Doppler Direct IR Laser Absorption Spectroscopy in Fast Ion Beams: The Fluorine Hyperfine Structure of HF+," J. Chem. Phys. 90 , 3893 (1989). 96. K.G. Lubic, D. Ray, D.C. Hovde, L. Veseth, and R.J. Saykally, "Laser Magnetic Resonance Rotational Spectroscopy of the Hydrogen Halide Molecular Ions: H79Br+," J. Mol. Spectrosc. 134, 21 (1989). 95. K.G. Lubic, D. Ray, D.C. Hovde, L. Veseth, and R.J. Saykally, "Laser Magnetic Resonance Rotational Spectroscopy of the Hydrogen Halide Molecular Ions: H35C1+ and H37C1+," J. Mol. Spectrosc. 134 , 1 (1989). 94. N.H. Rosenbaum, J.C. Owrutsky, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of HCS+: Analysis of Hot Bands and Perturbations," J. Mol. Spectrosc. 133 , 365 (1989). 93. K.B. Laughlin, G.A. Blake, R.C. Cohen, and R.J. Saykally, "Experimental Determination of Dipole Moments for Molecular Ions: Improved Measurements for ArH+," J. Chem. Phys. 90 , 1358 (1989). 92. J.V. Coe and R.J. Saykally, "Infrared Laser Spectroscopy of Molecular Ions," in Ion and Cluster Ion Spectroscopy and Structure , J.P. Maier, editor, Elsevier Science Publishers, pp. 131-154 (1989).

1988 Return to Publications Menu 91. M.B. Radunsky and R.J. Saykally, "Nonintrusive Measurement of Axial Electric Fields in Low Pressure Glow Discharges by Velocity Modulation Laser Spectroscopy," Chem. Phys. Lett. 152 , 419 (1988). LBL-23947 90. G. Blake, K.L. Busarow, R.C. Cohen, K.B. Laughlin, Y.T. Lee, and R.J. Saykally, "Tunable Far-Infrared Laser Spectroscopy of Hydrogen Bonds: The Ka=O(u)->1(g) Rotation-Tunneling Spectrum of the HC1 Dimer," J. Chem. Phys. 89 , 6577 (1988). LBL-25400 89. M.H.W. Gruebele, E. Keim, A. Stein, and R.J. Saykally, "Experimental Potential Functions for Open and Closed Shell Molecular Ions: Adiabatic and Nonadiabatic Corrections in X3[Sigma]- OH+ and X1[Sigma]+ ArH+," J. Mol. Spectrosc. 131 , 343 (1988). 88. R.C. Cohen, K.L. Busarow, K.B. Laughlin, G.A. Blake, M. Havenith, Y.T. Lee, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of van der Waals Bonds: Vibration-Rotation-Tunneling Spectra of Ar-H2O," J. Chem. Phys. 89 , 4494 (1988). LBL-25399 87. R.C. Woods and R.J. Saykally, "A Reanalysis of the Molecular Beam Electric Resonance Stark Effect Data for the a3[Pi] Carbon Monoxide," J. Chem. Phys. 89 , 2781 (1988). 86. K.L. Busarow, G.A. Blake, K.B. Laughlin, R.C. Cohen, Y.T. Lee, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy of van der Waals Bonds: Extended Measurements on the Lowest [Sigma] Bend of ArHC1," J. Chem. Phys. 89 , 1268 (1988). LBL-24859 85. M. Polak, M.H.W. Gruebele, G.S. Peng, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Negative Ions: the (011)-(001) Band of Azide (N3- )," J. Chem. Phys. 89 , 110 (1988). 84. R.L. Robinson, D.-H. Gwo, and R.J. Saykally, "Far Infrared Laser Stark Spectroscopy of the [Sigma] Bending Vibration of Ar-HC1: Strong Evidence for a Double Minimum Potential Surface," Molec. Phys. 63 , 1201 (1988). LBL-24806 83. R.J. Saykally, "Infrared Laser Spectroscopy of Molecular Ions," Science 239 , 157 (1988). 82. R.J. Saykally, T.A. Dixon, T.G. Anderson, P.G. Szanto, and R.C. Woods, "The Microwave Spectrum of CO in the a3[Pi] State. I. The J=O-1 Transitions in CO, 13CO, and C18O," J. Chem. Phys. 87 , 6423 (1987). 81. R.L. Robinson, D.-H. Gwo, and R.J. Saykally, "The High Resolution Far Infrared Spectrum of a van der Waals Stretching Vibration: The [nu]3 Band of Ar-HC1," J. Chem. Phys. 87 , 5156 (1987). LBL-23560

80. R.L. Robinson, D. Ray, D.-H. Gwo, and R.J. Saykally, "An Extended Study of the Lowest [Pi] Bending Vibration-Rotation Spectrum of Ar-HC1 by Intracavity Far Infrared Laser/Microwave Double Resonance Spectroscopy," J. Chem. Phys. 87 , 5149 (1987). LBL235459 79. K.B. Laughlin, G.A. Blake, R.C. Cohen, D.C. Hovde, and R.J. Saykally, "Determination of the Dipole Moments of Molecular Ions from the Rotational Zeeman Effect by Tunable Far Infrared Laser Spectroscopy," Phil. Trans. R. Soc. Lond. A, 234 , 109-119 (1988).

1987 Return to Publications Menu 78. J. Owrutsky, N. Rosenbaum, L. Tack, M. Gruebele, M. Polak, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Molecular Anions," Phil. Trans. R. Soc. Lond. A, 324, 97-108 (1987). 77. K.L. Busarow, G.A. Blake, K.B. Laughlin, R.C. Cohen, Y.T. Lee, and R.J. Saykally, "Tunable Far Infrared Laser Spectroscopy in a Planar Supersonic Jet: The [Sigma] Bending Vibration of Ar-H35C1," Chem. Phys. Letts. 141 , 289 (1987). LBL-23868 76. D.C. Hovde and R.J. Saykally, "Laser Magnetic Resonance in Supersonic Plasmas. The Rotational Spectrum of SH+," J. Chem. Phys. 87, 4332 (1987). 75. M. Polak, M.H.W. Gruebele, and R.J. Saykally, "Velocity Modulation Diode Laser Spectroscopy of Negative Ions: The [nu]1, [nu]1+ [nu]2-[nu]2, [nu]1+[nu]3-[nu]3 Bands of Thiocyanate (NCS- )" J. Chem. Phys. 87, 3352 (1987). 74. M.H.W. Gruebele, M. Polak, and R.J. Saykally, "A Study of the Structure and Dynamics of the Hydronium Ion by High Resolution Infrared Laser Spectroscopy. II. The [nu]4 Perpendicular Bending Mode of H316O+," J. Chem. Phys. 87 , 3347 (1987). 73. R.L. Robinson, D. Ray, D.-H. Gwo, and R.J. Saykally, "Vibration-Rotation Spectroscopy of ArHC1 by Far-Infrared Laser and Microwave/Far-Infrared Laser Double Resonance Spectroscopy," Sturcture and Dynamics of Weakly Bound Molecular Complexes , A. Weber, editor (D. Reidel Publishing Co., Dordrecht 1987) pgs. 85-92. LBL-22803 72. M.H.W. Gruebele, M. Polak, and R.J. Saykally, "Diode Laser Velocity Modulation Spectroscopy of Carbanions: The CC Stretching Vibration of C2H- ," J. Chem. Phys. 87, 1448 (1987). 71. M.B. Radunsky and R.J. Saykally, "Electronic Absorption Spectroscopy of Molecular Ions in Plasmas by Dye Laser Velocity Modulation: The A<-X System of N2+," J. Chem. Phys. 87 , 898 (1987). LBL #22177 70. M.H.W. Gruebele, M. Polak, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Negative Ions: The [nu]3, [nu]3+[nu]1-[nu]1, [nu]3+[nu]2-[nu]2, and [nu]3+2[nu]2-2[nu]2 Bands of Cyanate (NCO- )," J. Chem. Phys. 86 , 6631 (1987). 69. R.J. Saykally, K.M. Evenson, D.A. Jennings, L.R. Zink, and A. Scalabrin, "New FIR Laser Lines and Frequency Measurements for Optically Pumped CD3OH," Int. J. of Infrared and mm Waves, 8 , 653 (1987). 68. M. Polak, M.H.W. Gruebele, and R.J. Saykally, "Velocity Modulation Laser Spectroscopy of Negative ions: The [nu]3 Band of Azide (N3- )," J. Am. Chem. Soc. 109 , 2884 (1987). 67. Geoffrey A. Blake, K.B. Laughlin, R.C. Cohen, K.L. Busarow, and R.J. Saykally, "Laboratory Measurement of the Pure Rotational Spectrum of Vibrationally Excited HCO+ ([nu]2=1) by Far Infrared Laser Sideband Spectroscopy," Astrophys. J. 316 , L45 (1987). 66. R.L. Robinson, D.-H. Gwo, D. Ray, and R.J. Saykally, "Evidence for a Secondary Minimum in the ArHC1 Potential Surface from Far Infrared Laser Spectroscopy of the Lowest [Sigma] Bending Vibration," J. Chem. Phys. 86 , 5211 (1987). LBL-22804 65. K.B. Laughlin, G. A. Blake, R.C. Cohen, D.C. Hovde, and R.J. Saykally, "Determination of the Dipole Moment of ArH+ from the Rotational Zeeman Effect by Tunable Far Infrared Laser Spectroscopy," Phys. Rev. Letts. 58 , 996 (1987). 64. M.H.W. Gruebele, M. Polak, and R.J. Saykally, "Velocity Modulation Laser Spectroscopy of Negative Ions: The Infrared Spectrum of Hydrosulfide (SH- )," J. Chem. Phys. 86 , 1698 (1987).

1986 Return to Publications Menu 63. J.M. Brown, J.E. Schubert, R.J. Saykally, and K.M. Evenson, "The Far-Infrared Laser Magnetic Resonance Spectrum of the CF Radical and Determination of Ground State Parameters," J. Mol. Spectrosc. 120 , 421 (1986).

62. M.H.W. Gruebele, M. Polak, G.A. Blake, and R.J. Saykally, "Determination of the Born- Oppenheimer Potential Function of CC1+ by Velocity Modulation Diode Laser Spectroscopy," J. Chem. Phys. 85 , 6276 (1986). 61. A.L. Cooksy, R.J. Saykally, J.M. Brown, and K.M. Evenson, "Accurate Determination of the Fine Structure Intervals in the 3P Ground State of 13C and 12C by Far Infrared Laser Magnetic Resonance," Astrophys. J. Letts. 309 , 828 (1986). 60. L.M. Tack, N.H. Rosenbaum, J.C. Owrutsky, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy and Structure of the Amide Anion (NH2-)," J. Chem. Phys. 85 , 4222 (1986). 59. R.J. Saykally, K.M. Evenson, E. Comben, and J.M. Brown, "Measurement of the Rotational Spectrum of Carbon Monoxide in its Metastable a3[Pi] state by Laser Magnetic Resonance," Molec. Phys. 58 , 735 (1986). 58. S.E. Strahan, R.P. Meller and R.J. Saykally, "Measurement of the Rotational Spectrum of the Water Cation (H2O+) by Laser Magnetic Resonance Spectroscopy," J. Chem. Phys. 85 , 1252 (1986). LBL-21108 57. A.L. Cooksy, G.A. Blake, and R.J. Saykally, "Direct Measurement of the Fine Structure Interval and gJ Factors of Singly Ionized Atomic Carbon by Laser Magnetic Resonance," Astrophys. J. 305 , L89 (1986). 56. L.M. Tack, N.H. Rosenbaum, J.C. Owrutsky, and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Negative Ions: Measurement of the [nu]1 Vibration of Amide (NH2-)," J. Chem. Phys. 84 , 7056 (1986). 55.* R.J. Saykally, "Vibrational Spectroscopy of Negative Ions with Infrared Lasers," Spectroscopy, 1 , 40 (1986). *Cover Article. 54. A.L. Cooksy, D.C. Hovde, and R.J. Saykally, "Precise Measurement of the J = 2 <-1 Fine Structure Interval in N(II) by Far Infrared Laser Magnetic Resonance," J. Chem. Phys. 84 , 6101 (1986). 53. G.E. Scuseria, T.J. Lee, R.J. Saykally and H.F. Schaefer III, "Nitrogen Quadrupole Coupling Constants for HCN and H2CN+: Explanation of the Absence of Fine Structure in the Microwave Spectrum of Interstellar H2CN+," J. Chem. Phys. 84 , 5711 (1986). 52. N.H. Rosenbaum, J.C. Owrutsky, L.M. Tack, and R.J. Saykally, "Velocity Modulation Laser Spectroscopy of Negative Ions: The Infrared Spectrum of Hydroxide (OH- )," J. Chem. Phys. 84 , 5308 (1986). 51. M.H.W. Gruebele, M. Polak and R.J. Saykally, "Velocity Modulation of Vibrationally Excited CF+: Determination of the Molecular Potential Function," Chem. Phys. Letts. 125 , 165 (1986). 50.* R.J. Saykally and T. Van Slambrouck, "Infrared Spectroscopy of Molecular Cations and Anions with Color Center Lasers," Lasers and Applications , Vol. V , 80 (1986). *Cover Article. 49. M.H.W. Gruebele, R.P. Mller and R.J. Saykally, "Measurement of the Rotational Spectra of OH+ and OD+ by Laser Magnetic Resonance," J. Chem. Phys. 84 , 2489 (1986). LBL-20411. 48. D. Ray, R. Robinson, D.-H. Gwo and R.J. Saykally, "Intracavity Far Infrared Laser Spectroscopy of Supersonic Jets: Direct Measurement of the Vibrational Motions in van der Waals Bonds," J. Chem. Phys. 84 , 1171 (1986). LBL-20409. 47. J.C. Owrutsky, C.S. Gudeman, C.C. Martner, L.M. Tack, N.H. Rosenbaum and R.J. Saykally, "Determination of the Equilibrium Structure of Protonated Nitrogen by High Resolution Infrared Laser Spectroscopy," J. Chem. Phys. 84 , 605 (1986).

1984-1985 Return to Publications Menu 46. C.S. Gudeman, C.C. Martner and R.J. Saykally, "Electronic Spectroscopy of Molecular Ions by Velocity Modulation With CW Dye Lasers: A Non-Intrusvie, In Situ State- Selective Probe of Plasma Dynamics," Chem. Phys. Letts. 122 , 108 (1985). 45. J.C. Owrutsky, N.H. Rosenbaum, L.M. Tack, and R.J. Saykally, "The Vibration- Rotation Spectrum of the Hydroxide Anion (OH- ), J. Chem. Phys. 83 , 5338 (1985). 44. N.H. Rosenbaum, J.C. Owrutsky, L.M. Tack and R.J. Saykally, "Measurement of the [nu]1 Vibration-Rotation Spectrum of the Thioformyl Ion (HCS+) by Velocity Modulation Laser Spectroscopy," J. Chem. Phys. 83 , 4845 (1985). 43. C.A. Ferrari and R.J. Saykally, "Laser Magnetic Resonance Spectroscopy," Revista Brasileira de Fisica, 15 , 1, (1985).

42. D. Ray, R. Robinson, D.-H. Gwo, and R.J. Saykally, "Intracavity Far Infrared Laser Spectroscopy of Supersonic Jets: Direct Measurement of the Vibrational Motions in van der Waals Bonds," in Laser Spectroscopy , Vol. 7 (Y.R. Shen and T. Hansch, editors), Springer-Verlag, 1985. 41. M.H. Begemann and R.J. Saykally, "A Study of the Structure and Dynamics of the Hydronium Ion by High-Resolution Infrared Laser Spectroscopy, I. The [nu]3 Band of H316O+," J. Chem. Phys. 82 , 3570 (1985). 40. R.J. Saykally, "Laser Magnetic Resonance Rotational Spectroscopy," Chemistry in Britain, p. 159-161, February 1985. 39. D.J. Nesbitt, H. Petek, C.S. Gudeman, C.B. Moore and R.J. Saykally, "A Study of the [nu]1 Fundamental and Bend-Excited Hot Band of DNN+ by Velocity Modulation Absorption Spectroscopy with an Infrared Difference Frequency Laser," J. Chem. Phys. 81 , 5281 (1984). 38. E. Schafer and R.J. Saykally, "The High Resolution Infrared Spectrum and Molecular Structure of the Superacid H2F+ by Velocity Modulation Laser Absorption Spectroscopy," J. Chem. Phys. 81 , 4189 (1984). 37. C.S. Gudeman and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Molecular Ions," Ann. Rev. Phys. Chem. 35 , 387 (1984). 36. R.J. Saykally, "Studies of Astrophysically Important Molecular Ions with Ultrasensitive Infrared Laser Techniques," Molecular Astrophysics: State of the Art and Future Directions , ed. G.H. F. Diercksen, W.F. Huebner, and P.W. Langhoff (D. Reidel Pub. Co., 1985). 35. J. Pfaff, M.H. Begemann, and R.J. Saykally, "An Investigation of the Laser Optogalvanic Effect for Atoms and Molecules in Recombination-Limited Plasmas," Molec. Phys. 52 , 541 (1984). 34. L.M. Ziurys, D.P. Clemens, R.J. Saykally, M. Colvin, and H.F. Schaefer, "A Search for Interstellar Silicon Nitride," Astrophys. J. 281 , 219 (1984). 33. D.C. Hovde, E. Schafer, Susan E. Strahan, C.A. Ferrari, Douglas Ray, K.G. Lubic, and R.J. Saykally, "Measurement of the Rotational Spectrum of HF+ by Laser Magnetic Resonance," Molec. Phys. 52 , 245 (1984). 32. E. Schafer, R.J. Saykally, and Alan G. Robiette, "A High-Resolution Study of the [nu]3 Band of the Ammonium Ion (NH4+) by Velocity Modulation Laser Absorption Spectroscopy," J. Chem. Phys. 80 , 3969 (1984). 31. R.J. Saykally, Leif Veseth, and K.M. Evenson, "Laser Magnetic Resonance Rotational Spectroscopy of 2[Sigma] Radicals: Ethynyl (CCH)," J. Chem. Phys. 80 , 2247 (1984). 30. E. Schafer and R.J. Saykally, "Velocity Modulation Infrared Laser Spectroscopy of Molecular Ions: The [nu]1 and [nu]3 Bands of Fluoronium (H2F+)," J. Chem. Phys. 80 , 2973 (1984).

1980-1983 Return to Publications Menu 29. L.M. Ziurys, C. Henkel, and R.J. Saykally, "A Search for 2[Pi], N=1, J=3/2 Lambda- Doubling Transitions of CH," Astrophys. J. 275 , 175 (1983). 28. A.R.W. McKellar, P.R. Bunker, Trevor J. Sears, K.M. Evenson, R.J. Saykally, and S.R. Langhoff, "Far-Infrared Laser Magnetic Resonance of Singlet Methylene: Singlet- triplet perturbations, singlet-triplet transitions, and singlet-triplet splitting," J. Chem.Phys. 79 , 5251 (1983). 27. J. Pfaff, M.H. Begemann, and R.J. Saykally, "Visible Laser Optogalvanic Spectroscopy of a Hollow Cathode Plasma," proceedings on the International Conference on Lasers `82, December 1982. 26. M.H. Begemann, J. Pfaff, and R.J. Saykally, "Color Center Laser Optogalvanic Spectroscopy of a Planar Hollow Cathode Plasma," proceedings on the International Conference on Lasers `82, December 1982. 25. M.H. Begemann, C.S. Gudeman, J. Pfaff, and R.J. Saykally, "Detection of the Hydronium Ion (H3O+) by High-Resolution Infrared Spectroscopy," Phys. Rev. Lett. 51 , 554 (1983). 24. Eckhard Schafer, M.H. Begemann, C.S. Gudeman, and R.J. Saykally, "The Vibrational Spectrum of the Free Ammonium Ion (NH4+)," J. Chem. Phys. 79 , 3159 (1983). 23. C.C. Martner, J. Pfaff, Neil H. Rosenbaum, A. O'Keefe, and R.J. Saykally, "Radiative Lifetimes of Trapped Molecular Ions: HC1+ and HBr+," J. Chem. Phys. 78, 7073 (1983).

22. C.S. Gudeman, M.H. Begemann, J. Pfaff, and R.J. Saykally, "Tone-Burst Modulated Color Center Laser Spectroscopy," Optics Lett. 8, 310 (1983). 21. C.S. Gudeman, M.H. Begemann, J. Pfaff, and R.J. Saykally, "Velocity-Modulated Infrared Laser Spectroscopy of Molecular Ions: The v1 Band of HNN+," J. Chem. Phys. 78, 5837-5838 (1983). 20. R.J. Saykally, K.G. Lubic, K.M. Evenson, "Structures of Molecular Ions from Laser Magnetic Resonance Spectroscopy," Molecular Ions, edited by Joseph Berkowitz and Karl-Ontjes Groeneveld (Plenum Publishing Corp., 1983), pp. 33-52. 19. Christopher S. Gudeman, M.H. Begemann, J. Pfaff, and R.J. Saykally, "Velocity- Modulated Infrared Laser Spectroscopy of Molecular Ions: The v1 Band of HCO+," Phys. Rev. Lett. 50, 727 (1983). 18. Douglas Ray, K.G. Lubic, and R.J. Saykally, "The Laser Magnetic Resonance Spectrum of HC1+," Mol. Phys. 46, 217 (1982). 17. Lucy M. Ziurys, R.J. Saykally, R.L. Plambeck, and N.R. Erickson, "Detection of the N = 3-2 Transition of CCH in Orion and Determination of the Molecular Rotational Constants," Astrophys. J. 254, 94 (1982). 16. R.J. Saykally, Karen G. Lubic, A. Scalabrin, and K.M. Evenson, "The Pure Rotational Spectrum and Hyperfine Structure of CF Studied by Laser Magnetic Resonance," J. Chem. Phys. 77, 58 (1982). 15. M.H. Begemann and R.J. Saykally, "Color Center Laser Optogalvanic Spectroscopy of Lithium, Barium, Neon, and Argon Rydberg States in Hollow Cathode Discharges," Optics Commun. 40, 277 (1982). 14. R.J. Saykally, Marianne H. Begemann, and Jurgen Pfaff, "Optogalvanic Spectroscopy in Recombination-Limited Plasmas with Color Center Lasers," in Laser Spectroscopy V, edited by A.R.W. McKellar, T. Oka, and B.P. Stoicheff (Springer-Verlag 1981). 13. R.J. Saykally and R.C. Woods, "High Resolution Spectroscopy of Molecular Ions," Ann. Rev. Phys. Chem. 32, 403 (1981). 12. Artemio Scalabrin, R.J. Saykally, K.M. Evenson, Harrison E. Radford, and Masataka Mizushima, "Laser Magnetic Resonance Measurement of Rotational Transitions in the Metastable a 1&Mac198;g State of Oxygen," J. Mol. Spectrosc. 89, 344 (1981). 11. K.M. Evenson and R.J. Saykally, "Far-Infrared Laser Magnetic Resonance Spectroscopy," IAU Symposium #87 on Interstellar Molecules, B.H. Andrew, editor (Reidel Inc., Boston 1980). 10. P.G. Szanto, T.G. Anderson, R.J. Saykally, N.D. Piltch, T.A. Dixon, and R.C. Woods, "A Microwave Substitution Structure for Protonated Nitrogen N2H+," J. Chem. Phys. 75, 4261 (1981). 9. R.C. Woods, R.J. Saykally, T.G. Anderson, T.A. Dixon, and P.G. Szanto, "The Molecular Structure of HCO+ by the Microwave Substitution Method," J. Chem. Phys. 75, 4256 (1981). 8. K.M. Evenson, R.J. Saykally, Robert F. Curl, and J.M. Brown, "Far-Infrared Laser Magnetic Resonance," in Chemical and Biochemical Applications of Lasers, Vol. 5, C.B. Moore, editor (Academic Press, 1980). 7. R.J. Saykally and K.M. Evenson, "Direct Measurement of Fine Structure in the Ground State of Atomic Carbon by Laser Magnetic Resonance," Astrophys. J. 238, L107 (1980).

1975-1979 Return to Publications Menu 6. R.J. Saykally and K.M. Evenson, "Observation of Pure Rotational Transitions in the HBr+ Molecular Ion by Laser Magnetic Resonance," Phys. Rev. Lett. 43, 515 (1979). 5. R.J. Saykally and Kenneth M. Evenson, "Laser Magnetic Resonance Measurement of the 23P2 - 23P1 Splitting in Atomic Oxygen," J. Chem. Phys. 71, 1564 (1979). 4. T.G. Anderson, T.A. Dixon, N.D. Piltch, R.J. Saykally, P.G. Szanto, and R.C. Woods, "Laboratory Rest Frequencies of N2D+," Astrophys. J. 216, L85 (1977). 3. R.J. Saykally, T.A. Dixon, T.G. Anderson, P.G. Szanto, and R.C. Woods, "Laboratory Microwave Spectrum and Rest Frequencies of the N2H+ Ion," Astrophys. J. 205, L101 (1976). 2. R.J. Saykally, P.G. Szanto, Thomas G. Anderson, and R.C. Woods, "The Microwave Spectrum of Hydrogen Isocyanide," Astrophys. J. 204, L143 (1975).

1. R. Claude Woods, Thomas A. Dixon, Richard J. Saykally, and Peter G. Szanto, "Laboratory Microwave Spectrum of HCO+," Phys. Rev. Lett. 35, 1269 (1975). Return to the Publications Menu or the Saykally Group Homepage. Last Modified July 22 2002 knutsen@uclink4.berkeley.edu

R.J. Saykally Group Research Interests

I. NONLINEAR CHEMICAL IMAGING NANOMICROSCOPY(NCIN) Contact: Rich Schaller, Lynn Lee, Justin Johnson, Kelly Knutsen (510) 642-1047 We are developing novel optical imaging techniques primarily designed to characterize chemical interfaces, such as biological membranes and nanostructured films and materials. These combine the high spatial resolution of near-field scanning microscopy (NSOM) with the environmental and chemical specificity of resonantly enhanced nonlinear spectroscopy methods (e.g. sum frequency generation). This new effort has lead to the discovery of the first known tunable and reversible metal-insulator transition (in a film of silver nanoparticles) and a novel optical storage system via collaboration with the Heath group at UCLA, and the characterization of the "Worlds Smallest Laser"...a zinc oxide nanowire in collaboration with the Yang group at Berkeley. Several directions are being pursued: A. Structure and Function of Chloroplasts in Hydrogen-Producing Algae. An intriguing approach to a renewable, clean energy source is the generation of molecular hydrogen by photosynthetic algae. In a collaboration with the Mellis group at Berkeley, we are studying the structure and function of chloroplasts in such algae. Of particular interest is the alternative photosynthetic pathway adopted by these organisms when they are deprived of sulfur, which yields sustained hydrogen production. B. Structure and Properties of Luminescing Polymer Films. Luminescing polymers are of great current interest as electronic display media. The nanometric spatial variation of conjugation and its effects on excited electronic states of conjugated polymers influence their luminescing properties. NCIN provides a novel means of obtaining such information, and is pursued in collaboration with the Schwartz group at UCLA. Similar investigations of metal-doped polymers are underway in collaboration with the Chan group at the University of Hong Kong. Extensions to other types of polymer systems is envisioned. C. Organelle Evolution in the Cell Cycle. In collaboration with the Holman group at LBL, we are investigating the evolution of biochemical properties of individual organelles as a function of stage in the cell cycle with NCIN. Following single cell measurements of live human lung cells, we seek to exploit the infrared vibrational spectrum of specific biological structures for imaging individual organelles in living cells. Extension to various types of cancer cells in envisioned.

D. Structure and Function of Single Ion Channels. In collaboration with the Heath and Benzenilla groups at UCLA, and as the mission of Keck Institute for Chemical Imaging Microscopy, we are developing methods for imaging single K channels as a function of gating state, with the goal of deducing the specific molecular nature of the gating process. Extension to other types of ion channels is anticipated. E. Single Nanowire Lasers. The novel physics of zinc oxide nanowire lasers is investigated in collaboration with the Yang group at Berkeley, who recently discovered them. Single nanowires are imaged and the optical properties of active nanolasers are characterized by NCIN methods.

II. CHEMISTRY AND PHYSICS AT THE LIQUID WATER INTERFACE Contact: Kevin Wilson, Poul Petersen, Rich Schaller (510) 642-1047 The nature of then aqueous liquid/vapor interface in crucial to understanding a wide variety of phenomena in Nature. We are developing novel methods for characterizing the structure and dynamics of the liquid water surface and the nature of chemical reactions occurring thereon. Liquid microjet technology is employed to incorporate water and other volatile liquids into a soft X-ray spectrometer at the Lawrence Berkeley Advanced Light Source(ALS). Simultaneous detection of the total electron yield (TEY) and total ion yield (TIY) as a function of X-ray energy provides a direct comparative measure of electronic and geometrical structure of the bulk and surface, respectively. Extensions to aqueous solutions and to the study of chemical reactions on liquid surfaces are underway, using a combined X-ray/nonlinear spectroscopy approach.

III. SPECTROSCOPY AND DYNAMICS OF WATER CLUSTERS: TOWARD A COMPLETE MOLECULAR MODEL OF THE LIQUID Contacts: Serena Anderson, Heather Harker, Nir Goldman, Alex Huneycutt, Edwin Contreras (510) 642-1047 Using recently developed laser spectroscopy technology, the nature of small water clusters [(H2O)n, n = 2-10] is investigated in detail. The ultimate goal of this work is to utilize this highly detailed new information to develop a qualitatively improved model for liquid water. This is an important direction for computer simulations which involve water either explicitly or as a solvent. The project entails several complementary directions:

A. Terahertz Laser VRT Spectra of Water Clusters.

Currently, two sophisticated laser experiments are in operation for this purpose. We have measured very detailed spectra of the water dimer, trimer, tetramer, pentamer, and hexamer, which reveal much about the structures and hydrogen bond tunneling in these clusters. Analysis of the VRT spectra proceeds via extensive use of permutation - inversion group theory (the symmetric group). Future work will address sequentially larger clusters. Of particular interest in these studies is a quantification of cooperative effects on hydrogen bonding.

B. Determination of Intermolecular Potential Energy Surfaces (IPS). From the accurate measurement of intermolecular vibrational frequencies and cluster structures, we can determine the corresponding IPS with great accuracy and detail. This involves solving a high-dimensional (n &Mac179; 6) scattering problem with high accuracy and efficiency. New computational algorithms have been developed for this purpose, based on a highly efficient discrete variable representation for the intermolecular Hamiltonian. An IPS for the water dimer has recently been determined using these methods, and will seek to build on these results. C. Determination of an Effective Pair Potential For Liquid Water. From the knowledge of structures and cooperativity effects deduced from the spectra and IPS of water clusters, new effective pair potentials are being developed for describing liquid water in molecular dynamics simulations. D. Infrared Cavity Ringdown Spectroscopy. Using newly developed laser technology, we are studying water clusters in the mid-IR (OH stretch). Of interest in this endeavor is the quantification of the frequency shifts in covalent vibrations that accompany hydrogen bond formation, and characterization of the vibrational predissociation effected by the excitation of covalent vibrations. We are also interested in developing equilibrium sources for them such that chemical reactions and nucleation phenomenon involving water clusters can be addressed.

IV. MOLECULAR ASTROPHYSICS: CARBON IN THE UNIVERSE Contacts: Raphael Casaes, Alex Huneycutt (510) 642-1047 The form and distribution of carbon in the Universe is not well-known. As this element is crucial in the contexts of planetary formation and the evolution of life, it is an important goal of modern astrophysics to obtain such knowledge. We are carrying out both laboratory and observational astrophysics studies of two forms of carbon that may be abundant in the Universe pure carbon clusters (Cn) and polycyclic aromatic hydrocarbons (PAHs):

A. Infrared Laser Spectroscopy of Ultracold Carbon Clusters. A solid carbon sample is vaporized with a YAG laser into a supersonic expansion. The resulting cold (10K) carbon clusters are probed via vibration-rotation spectroscopy with IR cavity ringdown spectroscopy. From the detailed spectra obtained, accurate structures and bonding properties are extracted, essential for understanding how the nature of carboncarbon bonding evolves as the size of clusters increases. This work is being extended to silicon containing systems.

B. Observational Airborne Astronomy. Using the above laboratory data as a guide, searches are made for carbon clusters in interstellar dust clouds and stars. These will be carried out aboard the SOFIA Airborne Observatory with far infrared hetrodyne receivers, in collaboration with astronomers. Recently, the C3 molecule was detected for the first time in a cold dust cloud by this approach.

C. SPIRES: Identification of the Unidentified Infrared Emission Bands (UIR's). Many astrophysicists are currently concerned with identifying the nature of interstellar dust grains, which account for a considerable fraction of the total mass of interstellar dust clouds. The UIRs and associated Diffuse Interstellar Emission Bands (DIBs) found by astronomers are thought to be associated with such dust regions, and it is proposed that PAHs are their carriers. We have developed the SPIRES experiment (Single Photon InfraRed Emission Spectroscopy) for studying the IR emission accompanying UV laser excitation of large carbon molecules thought to be involved in the UIRs. Based on single photon counting detection of IR fluorescence, this approach permits access to much longer wavelengths than was previously possible. This will permit a definitive assessment of proposed models for explanation of the UIRs. We have thus far eliminated neutral PAHs as large as coronene as possible carriers of these features. Current work addresses ionized forms of PAHs, currently thought to be the best candidate for UIR carriers.

V. INFRARED CAVITY RINGDOWN LASER SPECTROSCOPY: A NEW ULTRASENSITIVE ABSORPTION TECHNIQUE FOR TRACE ANALYSIS Contacts: Raphael Casaes, Alex Huneycutt (510) 642-1047 Over the past few years, IR cavity ringdown spectroscopy has emerged as a simple but very powerful new means of probing trace species in direct absorption with extremely high sensitivity and microsecond time resolution. The exciting potential of this new laser technique is being explored for use

in measuring nucleation phenomenon, chemical reaction dynamics, reactive plasma dynamics, and the roles of trace species in combustion and atmospheric chemistry contexts. It has already been successfully used for studies of water and alcohol clusters, nucleotide bases, amino acids, and carbon clusters. Two new technical approaches are being pursued. A high spectral resolution spectrometer based on stimulated Raman shifting of a seeded Alexandrite laser will replace IR diodes and color center lasers, and a more conventional Raman shifted dye laser spectrometer is designed to reach longer wavelengths.

VI. SPECTROSCOPY OF DEEPLY SUPERCOOLED LIQUIDS Contact: Kevin Wilson (510) 642-1047 The nature of liquids in their "deeply supercooled" regions is a topic of much current interest. We are exploring new ways to supercool volatile liquids in high vacuum experiments. Infrared and Raman spectroscopy, X-ray absorption and scattering, and nonlinear IR spectroscopy experiments are pursued, using the LBL Advanced Light Source Facilities.

References: 1. R.S. Fellers, L.B. Braly, M.G. Brown, and R.J. Saykally, "Spectroscopic Determination of the Water Pair Potential," Science 284, 945 (1999). 2. R.J. Saykally, "Water Clusters: Building Up the Liquid One Step at a Time," Proceedings of the Nobel Symposium 117 on The Physics and Chemistry of Clusters, Visby, Sweden, E.E.B. Campbell and M. Larsson, editors, pp. 206-218 (2001). 3. A. Van Orden and R.J. Saykally, "Small Carbon Clusters: Spectroscopy, Structure, and Energetics," Chemical Reviews 98, 6, 2313-2357 (1998) - Cover Article. 4. K.R. Wilson, B. Rude, T. Catalano, R. Schaller, J.G. Tobin, D.T. Co, and R.J. Saykally, "X-Ray Spectroscopy of Liquid Water Microjets," J. Phys. Chem. B 105, 3346-3349 (2001) - Cover Article. 5. R.D. Schaller, J.C. Johnson, and R.J. Saykally, "Nonlinear Chemical Imaging Microscopy: Near-Field Third Harmonic Generation Imaging of Human Red Blood Cells," Analytical Chemistry 72, 5361-5364 (2000). 6. D.J. Cook and R.J. Saykally, "Simulated Infrared Emission Spectra of Highly Excited Polyatomic Molecules: A detailed model of the PAH-UIR hypothesis," Astrophys. J. 493, 793-802 (1998). 7. H.-S. Kim, D.R. Wagner, and R.J. Saykally, "Single Photon Infrared Emission Spectroscopy of the Gas Phase Pyrene Cation: Support for a Polycyclic Aromatic

Hydrocarbon Origin of the Unidentified Infrared Emission Bands," Phys. Rev. Lett. 86, 5691 (2001). 8. R.D. Schaller, and R.J. Saykally, "Near-field Sum Frequency Generation Imaging of CVD Zinc Selenide," Langmuir 17, 2055-2058 (2001). Return to the Saykally Group Homepage.
Last Modified 31 July 2001

"WATER BUCKYBALLS" CHEMICAL, CATALYTIC, AND COSMIC IMPLICATIONS Keith Johnson Massachusetts Institute of Technology; e-mail: kjohnson@mit.edu Summary Chemical, catalytic, and cosmic roles of pentagonal dodecahedral, "buckyball-like" water clusters are proposed, based on computed electronic structures and submillimeter-wavelength cluster vibrational modes. The cluster LUMOs are huge "s"-, "p"- and "d"- like orbitals that readily accept an extra electron. Dynamic Jahn-Teller orbital coupling to the submillimeter vibrational modes promotes water buckyballs as electron reservoirs in chemical and catalytic processes. The electronic and submillimeter vibrational spectra may explain certain diffuse interstellar bands, cosmic background radiation, and "missing cosmic baryonic matter". Cluster

oxygen-oxygen interactions in hydrogen bonding models of liquid and supercritical water are also discussed. A link to is included. -----------------------------------------------------------------------------------------------------------------------------------------Recent scientific interest in small water clusters has been motivated by their possible roles in atmospheric and environmental phenomena, as well as by their relevance to the structure and properties of liquid water and ice. Experiment and theory agree that not only can such clusters be produced, but also they exist optimally in certain numbers (so-called "magic numbers") and configurations of water molecules. Thus they deserve a significant place in the expanding field of cluster science. Prominent among the magic-number water clusters that have been identified are ones having a "buckyball-like" pentagonal dodecahedral structure. These clusters have a closed, ideally icosahedral symmetry formed by 20 hydrogen-bonded water molecules, with their oxygen atoms at the vertices of 12 concatenated pentagons and with 10 free exterior hydrogen atoms (Fig. 1(a)). Fig. 1(b) shows a (H2O)20H3O+ cluster, which occurs as a dominant molecular species in a variety of experiments. Its clathrate structure - a neutral water molecule trapped in the dodecahedral cage plus a relatively mobile proton has been the subject of previous theoretical discussions. This site is devoted to the electronic structure and

low-frequency vibrational modes of water "buckyballs", as well as to the implications of adding electrons to the clusters on their chemical, catalytic, and astrophysical properties. Although the oxygen atoms of neighboring water molecules are second-nearest neighbors, modest oxygen-oxygen "ppi"-orbital interactions are shown to play a key role, along with hydrogen bonding, in the electronic structures of these dodecahedral water clusters. They are shown to be largely responsible for the lowest frequency, submillimeter Hg "squashing" and Hu"twisting" vibrational modes of the dodecahedral cluster, indeed the lowest of any known cluster or molecule its size.
Fig. 1. (a) Pentagonal dodecahedral (H2O)20 cluster; (b) pentagonal dodecahedral ((H2O)20H3O+ cluster; (c) molecular orbitals of isolated H2O molecule; (d) (H2O)3 trimer; (e) interacting H2O molecular orbitals in (H2O)3.

Experimental evidence for submillimeter (5-150 cm-1) water cluster vibrational modes is discussed below. These symmetry-breaking cluster vibrations can be activated by the pseudo or dynamic Jahn-Teller (JT) effect, coupling with the water cluster electronic states to influence chemical and spectroscopic properties. There is a strong similarity between the JT properties of electrondoped dodecahedral water clusters and the JT-induced vibronic coupling believed by some scientists to underlie the superconductivity of doped solid buckminsterfullerene. The fact that the squashing and twisting vibrational frequencies (5-150 cm-1) of water buckyballs are much lower than the corresponding modes (250-1500 cm-1) of C60 is key to recognizing the submillimeter spectroscopic signatures of water buckyballs versus infrared spectra carbon buckyballs in interstellar space.

Fig 1(c) shows the occupied molecular orbitals for an isolated water molecule, as determined computationally and spectroscopically. Although the H2O "in-plane" b2 orbital has the largest bond overlap between an O atomic px-orbital and H atomic s-orbitals, notice should be taken of the practically nonbonding O(pz)-H(s) "in-plane" a1 orbital and the nonbonding O(py) "out-of-plane" b1 orbital. The b1 and b2 orbitals are the basis for modest O(px)-O(py)-O(px) "pi -bond" overlap between neighboring water molecules in clustered water, as illustrated schematically for a water trimer in Fig. 1(d) and (e). O(ppi )-O(ppi ) bond overlaps of this order of magnitude have been argued to trigger JT-induced anharmonic local electron-phonon coupling believed by some scientists to trigger high-Tc superconductivity in doped copper oxides. O - O nearest-neighbor interatomic distances (2.7-2.8A) in such materials are remarkably close to those of water. Semiempirical and density-functional molecular-orbital computations for the dodecahedral water clusters of Fig 1(a) and (b) holding an "extra" electron yield similar energy levels. Results for (H2O)20-1 are shown in Fig. 2.
Fig. 2. Molecular-orbital energies of a (H2O)20-1 cluster. The highest occupied "s" orbital (HOMO) and lowest unoccupied "p" and "d" orbitals (LUMOs) are spread around and radially extended away from the cluster "surface" oxygen atoms ( see Fig. 3). Spin polarization of the excess electron increases the HOMO LUMO energy. Deep "s"-, "p"- and "d"-bonding orbitals are localized within the cluster "cage". In uncharged (H2O)20, the cluster "s" surface orbital is the LUMO, separated from the O(2p) HOMO by a large energy gap. Similar results are obtained for (H2O)20H3O and (H2O)20H3O+ clusters.

The highest occupied molecular orbital (HOMO) of the "hydrated" electron is the gigantic cluster "s-orbital" mapped in Fig. 3(a). This is a spherical shell arising from O(ppi)-O(ppi)-O(ppi) atomic orbital overlap around the cluster "surface". The lowest unoccupied molecular orbitals (LUMOs) correspond to

huge, nearly degenerate px, py, and pz orbitals, one of which is mapped in Fig. 3(b). These "Rydberg-like" LUMOs also arise from O(ppi)-O(ppi)-O(ppi) atomic orbital overlap around the water cluster surface. They are bound states with a HOMO-LUMO (Cluster "s"-"px,py,pz") excitation energy of 1.8eV, consistent with spectroscopic studies of somewhat larger negatively charged water clusters. Spin polarization of the excess electron increases the HOMOLUMO energy to 5.9eV. Excitations from the s-like HOMO to the higher lying unoccupied cluster "d" levels shown in Fig. 2 and mapped in Fig. 3(c) are forbidden by the selection rules. The "s"-HOMO-"p"-LUMO excitations, as well as higher-energy (ultraviolet and x-ray) transitions from and to the O(2p), H-O bonding and deep-lying cluster "s"- and "p"- bonding levels in Fig. 2 may have astrophysical spectroscopic significance (see below). Because of the "extra" electron, (H2O)20-1 and (H2O)20H3O clusters are paramagnetic.

Quantum chemical computations of the vibrational modes for the hydratedelectron pentagonal dodecahedral clusters in Figs. 1(a) and (b) have also been carried out. Fig. 3(d) shows one of the lowest-frequency vibrational modes for cluster 1(b). This is a symmetry-breaking Hg "squashing mode" of the otherwise ideal icosahedrally symmetric pentagonal dodecahedral cluster, with a large-amplitude vibration of the clathrated hydronium oxygen atom coupled to breathing vibrations of the cluster surface oxygen atoms. For both clusters 1(a) and (b), these modes are calculated to occur in the very low frequency (submillimeter wavelength) range between 5 cm-1 and 50 cm-1.
Fig. 3. (a) "s"-like HOMO wavefunction of a (H2O)20-1 pentagonal dodecahedral cluster; (b) "p"-like LUMO wavefunction of a (H2O)20-1 cluster; (c) higher-energy unoccupied "d"-like (H2O)20-1 cluster wavefunction; (d) "Hg squashing" vibrational mode of a (H2O)20H3O buckyball in the frequency range 5-50 cm-1; (e) "Hg squashing" vibrational mode of (H2O)20H3O buckyball near 50 cm-1; (f) "Hu twisting" vibrational mode of (H2O)20H3O buckyball near 90 cm-1. Vibrational vectors are indicated by the arrows.

Fig. 3(e) shows another Hg cluster squashing mode around 50 cm-1. Fig. 3(f) shows an Hu cluster "twisting mode" near 90 cm-1. These extremely low frequency vibronic modes owe their existence to the flexing of the dodecahedral water cluster "surface" O O O bonds associated with adjacent 3-coordinated water molecules. This is consistent with recent He atom scattering studies of the surface vibrations of large water clusters, which show O O O "bending" modes at 5 meV (40cm-1) associated with adjacent 3-coordinated water molecules on the cluster surface. The hydrogen bond flexing and stretching vibronic modes are calculated to occur, as expected, at much higher frequencies. While ordinary bulk liquid water is not usually thought of as an "active" substance, water clusters, especially small symmetrical hydrated-electron clusters like the ones shown in Fig.1(a) and (b), are another matter due to the effectively large reactive cross sections of the cluster surface delocalized oxygen orbitals mapped in Fig. 3. Indeed, experimental studies of the thermal energy chemical reactions of size-selected hydrated-electron clusters (H2O)n-1 attribute their strong reactivity to the spatial delocalization of the excess electron at the cluster surface. Thus charged water clusters can function as electron reservoirs for chemical reactions involving electron transfer to or from the reacting species. In the oxidation of carbon compounds, such as occurs in hydrocarbon fuel combustion or biological cell metabolism, watercluster hydrated-electron delocalized orbitals, originating on the cluster surface oxygen atoms, can readily overlap with the reactive fuel carbon (e.g. ppi) orbitals, promoting oxidation. The proximity of the highest occupied dodecahedral water cluster excess-electron "s" orbital to the lowest unoccupied, nearly degenerate cluster "px,py,pz" orbitals (Fig. 2) suggests the strong possibility of coupling between the hydrated electron and the abovedescribed low-frequency cluster Hg vibrational modes via the pseudo or dynamic JT effect. The Hg cluster squashing modes associated with the

icosahedral symmetry are known to be JT-active in the case of electrondoped C60-1. JT coupling in the water clusters 1(a) and (b) leads to a prescribed symmetry breaking of the pentagonal dodecahedron along the low-frequency Hg vibronic squashing mode coordinates Qs, lowering the cluster potential energy from A to the equivalent minima A shown in Fig. 4. Because of the large JT-induced vibronic displacements (large Qs) of watercluster surface oxygen atoms in the Hg modes, the energy barrier for expulsion of water oxygen or OH radicals and their oxidative addition to reactive carbon atoms is lowered from Ebarrier to Ebarrier, as shown in Fig. 4. The practical use of hydrated-electron water clusters to break down and more completely burn particulate matter (smoke/soot) precursor molecules, as well as serving as a combustion oxygenate in fossil fuels, has recently been demonstrated by this author and described in U.S. Patents Nos. 5,800,576 and 5,997,590.

Fig. 4. Schematic potential energy curves showing how pseudo/dynamic Jahn-Teller coupling of water buckyball HOMO-LUMO electron orbitals in Fig. 3(a)-(c) with the cluster low-frequency vibronic modes in Fig. 3(d)-(e) can, in principle, lower the energy barrier for a chemical reaction along reaction coordinates Qs corresponding to the symmetry-determined vibronic modes (see ref. 29).

Polyhedral water clusters, especially concatenated pentagonal clusters, have been experimentally identified as being key to the hydration of biomolecules. It has even been suggested that water clusters may play a fundamental role in biological cell architecture. In such scenarios, the cluster surface oxygen-based molecular orbitals and JT-induced low-frequency vibrational modes described above most likely underlie the active roles of water in biology. On a cosmic scale, the electronic and submillimeter vibrational spectra of pentagonal dodecahedral water buckyballs may help to solve the long-

standing mystery of "diffuse interstellar bands" (DIBs). DIBs are optical absorption features in stellar spectra observed through dense interstellar material. Of the many encountered DIBs thus far, only a few have been tentatively identified molecularly. A key feature of the notorious DIBs near wavelength 6800A is an intriguing regularity in the frequencies of the stronger spectral lines, namely a spacing of about 35cm-1, suggesting a molecular vibrational component at that frequency. Speculations that C60 buckyballs, polycyclic aromatic hydrocarbons (PAHs), or other polycarbon chains may be responsible for the DIBs are hampered by the fact that the lowest C-C and C-H vibrational frequencies of these species are much higher than 35cm-1. As mentioned above, "excess-electron" water buckyballs have lowest-energy HOMO-LUMO optical absorption around 1.8eV, i.e. in the region of the 6800A DIBs, and lowest Hg squashing vibronic modes in the vicinity of the 35cm-1 DIB line spacing ascribed to molecular vibrations. Experimental evidence cited above for vibrations near this frequency in (H2O)n clusters between n = 20-100 has recently been reported. Considering the laboratory stability of water buckyballs at the magic numbers 20 and 21 and their anticipated stability in the cold of interstellar space, they are likely candidates for sources of unexplained DIB spectra. The 5.9 eV HOMO- LUMO energy of a "spin-polarized" excess electron on a water buckyball (Fig. 2) corresponds approximately (and perhaps coincidentally) to the notorious and thus far unidentified 2175A interstellar absorption feature. Evidence for significant quantities of water "vapor" in nebulae, stellar atmospheres, and planetary objects has grown in recent years. Much of this evidence is based on the signature of the infrared O-H "stretching" and "bending" vibrational modes common to individual water molecules. Vibronic modes arising from H-O bonding also occur in water clusters, so at least some of the observed water vapor may actually be present in the form of water buckyballs. Given that oxygen is the third most abundant cosmic element, following hydrogen and helium and preceding carbon, it is tempting to speculate on the more general cosmic significance of water buckyballs. Recent infrared observations of a water-generating gas cloud in the Orion nebula confirm theories of how shock waves emanating from star formation heat the gas and speed up chemical reactions causing free hydrogen and oxygen to combine into water. Considering evidence that the shocks are creating water at an enormous rate, it is likely that water buckyballs are a plentiful interstellar product. Since star formation occurs in galaxies throughout the universe, the cosmic abundance of water buckyballs is a compelling possibility. Mass spectra of the carbonaceous residue in impact craters on the Long Duration Exposure Facility (LDEF) spacecraft have provided evidence for the occurrence of C60 and C70 buckyballs in space. Collisions between chemically reactive charged water and carbon buckyballs in space and under the influence of cosmic radiation could produce some of the many organic species observed in nebulae.

Capture of cosmic-ray electrons by neutral (H2O)20 and/or (H2O)20`H3O+ clusters may occur naturally in space due to the large capture cross sections of the cluster LUMOs. If cosmic electrons are traveling close to the speed of light, their interaction with the above-described low-frequency cluster vibronic modes could result in the conversion of the associated watercluster far-infrared radiation to x-ray or gamma radiation via the inverse Compton effect (ICE). A recent report of statistical observational evidence for a "gamma-ray halo" surrounding our Milky Way galaxy attributes the halo either to the ICE or to "dark matter". If water buckyballs are responsible for certain DIB spectra, then they are also candidates for ICE-induced galactic gamma radiation. Selection-rule-allowed electronic transitions between the ionized water cluster deep-lying "s"-, "p"- and "d"-bonding levels and HOMO-LUMO "s", "p" and "d" levels in Fig. 2 are consistent with increasing evidence for lowenergy x-ray emissions from some unknown vast filamentary network of "high-temperature baryonic gas/plasma" linking galaxies and galaxy clusters. Cosmic water buckyballs and their paramagnetic ions, could therefore be viewed as one possible species of "missing baryonic matter". Perhaps data from the Submillimeter Common User Bolometric Array (SCUBA), which has recently detected striking far-infrared emission from distant star-forming galaxies in the very-low-frequency range of the abovedescribed water buckyball vibrations, could be utilized to help confirm these conjectures. In view of the emphasis placed here on the consequences of oxygen-oxygen interactions in pentagonal dodecahedral water clusters, it is natural to consider their possible relevance to the properties of and traditional hydrogen-bonding models for liquid water. Linus Pauling originally pointed out that "pentagonal dodecahedra may be arranged relative to one another in a large number of ways, so that highly random structures for liquid water might be based upon aggregates of water molecules bonded to one another in this way." Because of the tetrahedral coordination of hydrogen-bonded pentamers in such a model, it may be viewed as an extension of the conventional tetrahedral structural scenario for liquid water to include O O - O interactions. Low-frequency Raman scattering studies of liquid water reveal a broad band between 5 and 100 cm-1 with a maximum at 50cm-1 for a temperature of 20oC. This band has been attributed to "flexing" vibrations of O O - O units in water clusters having an effective Raman scattering crosssection of 11A at 20oC. If one adds the large amplitudes of the abovedescribed Hg vibronic modes of a water dodecahedron to its equilibrium diameter, the Raman-implied 11A size is in accord with a dynamical dodecahedral model for liquid water. Raman measurements for both O16 and O18 isotopes of liquid water reveal a significant isotope shift of this lowfrequency peak, consistent with the oxygen-derived vibrational modes of the dodecahedron. Delocalized O O - O ppi-bond overlap occurs not only around the surface of an individual dodecahedral water cluster but can also

take place between connected dodecahedra in Paulings model of liquid water. The observation that neighboring water molecule H s-orbitals are in a bonding phase relationship with the O ppi orbitals (Fig. 1e) suggests that dynamical O O - O ppi-bond overlap effectively "propagates" hydrogen bonding over long distances in liquid water. Thus hydrogen bonding between water molecules may not be a purely local "electrostatic" sharing of a proton, as conventionally viewed, but is effectively delocalized via the second-neighbor O O - O ppi-bond overlap. This "many-body" electronic effect, JT-coupled with the calculated and measured low-frequency O O - O vibrations, may explain the unique and still poorly understood properties of liquid water, such as its large heat capacity and anomalous freezing properties. The large heat of vaporization of liquid water may also be related to delocalization of hydrogen bonding via the O O O interactions. If interacting water-cluster O O O ppi-electrons and low-frequency vibrations are relevant to the properties of liquid water at ordinary atmospheric pressure and temperature, it is likely that they also play key roles at the high pressures and temperatures of supercritical water. In fact, it has been deduced from x-ray and neutron diffraction studies of supercritical water that its extraordinary physical and chemical properties are associated with increased O O bonding at the expense of significantly decreased hydrogen bonding due to water molecule clustering. In conclusion, it is suggested from quantum chemistry and available experimental information that pentagonal dodecahedral water clusters may play active roles in a wide range of chemical, catalytic, biological, and astrophysical scenarios. Furthermore, the technological use of such water clusters to enhance combustion and significantly reduce pollutants in fossil fuels has recently been demonstrated. See for a description of an entertaining feature film and television series in which water plays a key role.

Ver AGUA MEMORIA MOLECULAR - Water structure and behavior.EXE (de Martin Chaplin) Ver AGUA Dr.Jacques Benveniste DigiBios.DOC

Scientists may have found homeopathy proof

A researcher's chance finding in a lab may finally prove homeopathy works.

Scientists in South Korea were shocked to find no matter how much they diluted a solution the more the molecules inside clustered together. Homeopaths repeatedly dilute their medications believing that is what makes them stronger. Scientists had expected the fullerene molecules in their solution to spread out but they did the opposite. New Scientist reports this discovery could provide the first insight into how homeopathy works. The phenomenon was discovered by German chemist Kurt Geckeler and his colleague Shasadhar Samal at the Kwangju Institute of Science and Technology. It worked only in so-called polar solvents like water, in which one end of the molecule has a strong positive charge and the other has a negative one. The finding indicates diluting homeopathic remedies may increase the size of the particles so they become biologically active. Mr Geckeler said: "We want people to repeat it. If it's confirmed it will be groundbreaking." Story filed: 19:06 Wednesday 7th November 2001

Bizarre chemical discovery gives homeopathic hint

19:00 07 November 01

It is a chance discovery so unexpected it defies belief and threatens to reignite debate about whether there is a scientific basis for thinking homeopathic medicines really work. A team in South Korea has discovered a whole new dimension to just about the simplest chemical reaction in the book - what happens when you dissolve a substance in water and then add more water. Conventional wisdom says that the dissolved molecules simply spread further and further apart as a solution is diluted. But two chemists have found that some do the opposite: they clump together, first as clusters of molecules, then as bigger aggregates of those clusters. Far from drifting apart from their neighbours, they got closer together. The discovery has stunned chemists, and could provide the first scientific insight into how some homeopathic remedies work. Homeopaths repeatedly dilute medications, believing that the higher the dilution, the more potent the remedy becomes. Some dilute to "infinity" until no molecules of the remedy remain. They believe that water holds a memory, or "imprint" of the active ingredient which is more potent than the ingredient itself. But others use less dilute solutions - often diluting a remedy six-fold. The Korean findings might at last go some way to reconciling the potency of these less dilute solutions with orthodox science.

Completely counterintuitive

German chemist Kurt Geckeler and his colleague Shashadhar Samal stumbled on the effect while investigating fullerenes at their lab in the Kwangju Institute of Science and Technology in South Korea. They found that the football-shaped buckyball molecules kept forming untidy aggregates in solution, and Geckler asked Samal to look for ways to control how these clumps formed. What he discovered was a phenomenon new to chemistry. "When he diluted the solution, the size of the fullerene particles increased," says Geckeler. "It was completely counterintuitive," he says. Further work showed it was no fluke. To make the otherwise insoluble buckyball dissolve in water, the chemists had mixed it with a circular sugar-like molecule called a cyclodextrin. When they did the same experiments with just cyclodextrin molecules, they found they behaved the same way. So did the organic molecule sodium guanosine monophosphate, DNA and plain old sodium chloride. Dilution typically made the molecules cluster into aggregates five to 10 times as big as those in the original solutions. The growth was not linear, and it depended on the concentration of the original. "The history of the solution is important. The more dilute it starts, the larger the aggregates," says Geckeler. Also, it only worked in polar solvents like water, in which one end of the molecule has a pronounced positive charge while the other end is negative.
Biologically active

But the finding may provide a mechanism for how some homeopathic medicines work something that has defied scientific explanation till now. Diluting a remedy may increase the size of the particles to the point when they become biologically active. It also echoes the controversial claims of French immunologist Jacques Benveniste. In 1988, Benveniste claimed in a Nature paper that a solution that had once contained antibodies still activated human white blood cells. Benveniste claimed the solution still worked because it contained ghostly "imprints" in the water structure where the antibodies had been. Other researchers failed to reproduce Benveniste's experiments, but homeopaths still believe he may have been onto something. Benveniste himself does not think the new findings explain his results because the solutions were not dilute enough. "This [phenomenon] cannot apply to high dilution," he says. Fred Pearce of University College London, who tried to repeat Benveniste's experiments, agrees. But it could offer some clues as to why other less dilute homeopathic remedies work, he says. Large clusters and aggregates might interact more easily with biological tissue.

Double-check

Chemist Jan Enberts of the University of Groningen in the Netherlands is more cautious. "It's still a totally open question," he says. "To say the phenomenon has biological significance is pure speculation." But he has no doubt Samal and Geckeler have discovered something new. "It's surprising and worrying," he says. The two chemists were at pains to double-check their astonishing results. Initially they had used the scattering of a laser to reveal the size and distribution of the dissolved particles. To check, they used a scanning electron microscope to photograph films of the solutions spread over slides. This, too, showed that dissolved substances cluster together as dilution increased. It doesn't prove homeopathy, but it's congruent with what we think and is very encouraging," says Peter Fisher, director of medical research at the Royal London Homeopathic Hospital. "The whole idea of high-dilution homeopathy hangs on the idea that water has properties which are not understood," he says. "The fact that the new effect happens with a variety of substances suggests it's the solvent that's responsible. It's in line with what many homeopaths say, that you can only make homeopathic medicines in polar solvents." Geckeler and Samal are now anxious that other researchers follow up their work. "We want people to repeat it," says Geckeler. "If it's confirmed it will be groundbreaking". Journal reference: Chemical Communications (2001, p 2224) Andy Coghlan ITALIAN TRANSLATE
Il Science & Technology News Service n. 1 nel mondo

Una strana scoperta chimica

7 Nov. 2001 Andy Coghlan Si tratta di una scoperta avvenuta per caso, cosi' inattesa, che sfida la convinzione e minaccia di riaccendere il dibattito sul fatto se ci sia una base scientifica nel pensare che le medicine omeopatiche funzionano veramente. Un'equipe in Sud Africa ha scoperto un aspetto del tutto nuovo a proposito della reazione chimica piu' semplice - quello che avviene quando si scioglie una sostanza nell'acqua e poi si aggiunge altra acqua.

La scienza convenzionale afferma che quando una soluzione viene diluita, le molecole dissolte si disseminano. Ma due chimici hanno riscontrato che qualcuna si comporta diversamente: esse si ammucchiano insieme, prima in grappoli di molecole, poi come aggregati piu' grandi di grappoli. Esse non si allontanano da quelle vicine, ma si avvicinavano sempre piu'. La scoperta ha meravigliato i chimici e potrebbe offrire un primo approccio scientifico su come certe cure omeopatiche funzionano. Gli omeopati ripetutamente diluiscono i farmaci, credendo che piu' la diluizione e' elevata piu' la cura diventa efficace. Alcuni diluiscono all' "infinito" fino a quando non resta alcuna molecole della cura. Essi credono che l'acqua abbia una memoria o un "imprint" dell'ingrediente attivo che e' piu' potente dello stesso ingrediente. Ma altri usano soluzioni meno diluite - spesso diluendo per sei volte la cura. Le scoperte coreane potrebbero alla fine andare a riconciliare l'efficacia di queste soluzioni meno diluite con la scienza ortodossa. Contro l'intuizione Il chimico tedesco Kurt Geckeler ed il suo collega Shashadhar Samai si sono imbattuti per caso sul risultato mentre investigavano sul "fullerene" nel loro laboratorio di Scienze e Tecnologia di KwangJi in Sud Corea. Essi Hanno scoperto che le molecole a forma di palla da football continuavano a formare aggregati disordinati nella soluzione, e Geckler chiese a Samai di cercare i modi per regolare la formazione di questi blocchi. Quello che ha scoperto e' stato un fenomeno nuovo nella chimica. "Quando egli ha diluito la soluzione, e' aumentata la dimensione delle particelle fullerene" ha detto Geckler. "Si andava completamente contro l'intuizione," ha dichiarato. Il lavoro successivo mostrava che non si trattava di un colpo di fortuna. Per far dissolvere l'altra parte diversa di molecole insolubili nell'acqua, i chimici l'avevano mischiata con una molecola circolare come lo zucchero chiamata cyclodextrin. Quando fecero lo stesso esperimento solo con molecole cyclodextrin, essi riscontrarono che si comportavano allo stesso modo. Cosi' faceva il monofosfato "guanosine" di sodio della molecola organica, il DNA e il cloruro di sodio. La diluizione trasformava i grappoli di molecole in aggregati da 5 a 10 volte grandi quanto quelli delle soluzioni originali. La crescita non era lineare e dipendeva dalla concentrazione dell'originale. "La storia della soluzione e' importante. Piu' inizia la diluizione piu' grandi sono gli aggregati," ha detto Geckler. Inoltre funzionava solo nei solventi polari come l'acqua, dove un'estremita' della molecola ha una carica positiva pronunciata mentre l'altra estremita' e' negativa. Biologicamente attivo Ma la scoperta puo' fornire un meccanismo per il funzionamento di alcune medicine omeopatiche - qualcosa che ha sfidato la spiegazione scientifica fino ad oggi. Diluire una cura puo' aumentare la dimensione delle particelle fino al punto di diventare biologicamente attive. Inoltre essa fa da eco alle controverse dichiarazioni dell'immunologo francese Jacques Benveniste. Nel 1988

Benveniste dichiaro' in un articolo di "Nature" che una soluzione che aveva contenuto una volta degli anticorpi attivava ancora i globuli bianchi umani. Benveniste ha dichiarato che la soluzione funzionava ancora perche' conteneva "imprints" fantasma nella struttura dell'acqua dove erano stati gli anticorpi. Altri ricercatori hanno fallito nel riprodurre gli esperimenti di Benveniste, ma gli omeopati credono ancora che egli fosse giunto a qualche risultato. Lo stesso Benveniste non pensa che le nuove scoperte spiegano i suoi risultati perche' le soluzioni non erano abbastanza diluite. "Questo fenomeno non si puo' applicare ad una diluizione elevata " ha detto. Fred Pearce dell'Universita' College di Londra, che cerco' di ripetere gli esperimenti di Benveniste, concorda. Ma esso puo' offrire degli indizi come al perche' altre cure omeopatiche meno diluite funzionano, ha detto. Grandi grappoli e aggregati possono interagire piu' facilmente con il tessuto biologico. Un doppio controllo Il chimico Jan Enberts dell'Universita' di Groningen in Olanda e' piu' cauto. "E' ancora una questione del tutto aperta" ha detto. "Dire che il fenomeno ha un significato biologico e' pura speculazione". Ma egli non ha dubbi sul fatto che Samai e Geckler abbiano scoperto qualcosa di nuovo. "E' sorprendente e preoccupante " ha detto. I due chimici erano alle prese nel controllare due volte i sorprendenti risultati. Inizialmente essi utilizzarono il laser per rivelare la dimensione e la distribuzione delle particelle dissolte. Poi per verificare essi usarono un microscopio elettronico per fotografare la diffusione delle soluzioni sui vetrini. Anche questo ha dimostrato che sostanze dissolte si aggregano insieme quando aumenta la diluizione. "Non dimostra l'omeopatia, ma corrisponde a quello che pensiamo ed e' molto incoraggiante" ha dichiarato Peter Fisher, direttore delle ricerche mediche all'Ospedale Omeopatico Royal di Londra. "L'idea di un omeopatia ad elevata diluizione dipende dall'idea che l'acqua ha proprieta' non comprese" ha detto. "Il fatto che il nuovo risultato si abbia con varie sostanze suggerisce che il solvente sia il responsabile. E' in linea con quello che molti omeopati affermano che si possono solo fare medicine omeopatiche in solventi polari". Geckler e Samai desiderano fortemente che altri ricercatori seguano il loro lavoro. "Vogliamo che le persone lo ripetano" ha detto Geckler. "Se esso verra' confermato rappresentera' una scoperta" Giornali di riferimento: Chemical Communications (2001 p 2224) 7 Nov. 2001 (su "NewScientist.com" del 07.11.2001)