Copy of the article in Physics News, Vol.39, Nos.2, pp.

5-14, April 2009 Published by the Indian Physics Association

AFragmentaryTaleoftheAtom i BicentennialTribute to JohnDaltonsANewSystemofChemicalPhilosophy(1808) PCDeshmukh*andShyamalaVenkataraman DepartmentofPhysics,IndianInstituteofTechnologyMadras Chennai600036 *pcd@physics.iitm.ac.in I. Introduction:

RichardFeynmanchosetheatomichypothesistobethemostimportantsinglestatementtobepassed ontoposterityifonlyonesentencewouldoutliveacatastropheinwhichallelsewouldperish.Thiswell knownhypothesis,isthatAllthingsaremadeofatomslittleparticlesthatmovearoundinperpetual motion,attractingeachotherwhentheyarealittledistanceapart,butrepellinguponbeingsqueezedinto one another. The beginnings of this idea are traced to John Daltons hypothesis made in 1808 that all matterconsistsoftiny,indivisibleparticles,calledatoms.TwohundredyearshaveelapsedsinceDaltons publicationofANewSystemofChemicalPhilosophy.Itisinterestingatthispointtoreflectonhowthe atomistic model has grown, providing insights in fundamental laws of nature, and producing modern gadgets that have pushed the frontiers of technology at an incredible pace. Mans exploration in the physicsoftheatomcontinuestoprovidenewinsightsinthefundamentallawsofphysics.Asynopsisof thedevelopmentsofatomicscienceovertwohundredyearsisbothanexcitingandachallengingtask, evenifonlyaveryfewofitsselectfragmentscanscarcelybetouchedupon.Thistalewillattemptjust that. Analysisofthephysicalworldintermsofthetiniestofthematerialparticlesisinfactveryold,anancient one. In fact, it precedes Daltons revolutionary system of chemical philosophy [1]. The first known conception of the atomistic approach to the material world is perhaps found in the works of Maharshi Kanad(600BC)whodevelopedtheVaisesikaphilosophy.Inthisphilosophy,theatomisticmodelofthe materialworldispropounded.HowevertheVaisesikaphilosophygoeswellbeyondthematerialworld anditseekstoexplorethecognizablematerialuniverseintermsofnineelements:air,earth,fire,mind, self,sky,space,timeandwater.MaharshiKanadscontributionstoscientificanalysisoftheuniverseare extensive.TheBrahmaVaivartPuraninfactnarratesthatMaharshiKanadwasareincarnationofSage Gautama,whowasordainedbyLordShivahimselftoreappearintheroleofKanad. InthepostGalileoNewtonperiod,theatomisticmodelwaspropoundedalongamodernanalytical scientificapproachbyJohnDalton,bornonthe6thofSeptember1766atEaglesfield,Cumberland,in England.Daltonsearlyworkincludedmaintainingmeteorologicalrecordsandheevenpublisheda book on English grammar, which earned him membership of the Manchester Literary and PhilosophicalSociety.Hereportedextensivelyoncolorblindness,whichafflictedbothhimandhis

brother, and often referred now as Daltonism. Dalton investigated several principles in chemistry andthermodynamicsandwentontoformulatehisatomicmodelofcondensedmatterwhichwas recognized and included by Dr. Thomas Thomson, Professor of Chemistry at the University of Glasgow,intheIIIEditionofhisbookASystemofChemistry,publishedin1807.Thisworkcamein the exciting period hailed as one in which chemistry achieved maturity as a science [2]. An excellentreviewofDaltonscontributionsandhispersonalitycanbefoundinthereviewbyBolton [3].JohnDaltonisamongstthemostcelebratedchemists.ThiscanbeseenfromthefactthattheRoyal Society of Chemistry, which came into being through an amalgamation of four very prestigious academic bodies [(i)The Chemical Society (founded in 1841), (ii) The Society for Analytical Chemistry(foundedin1874),(iii)TheRoyalInstituteofChemistry(foundedin1877)and(iv)The FaradaySociety(foundedin1903)]publishesajournalnamedDaltonTransactions.Thisisthemost prestigiouspublicationoftheRSCandhasthehighestimpactfactoramongsttheEuropeanjournals inthefieldofinorganic,bioinorganicandorganometallicchemistry. EssentialelementsofJohnDaltonsatomisticvieware containedinthefollowingpostulateshemadeabout theatomnamely: Matterconsistsoftiny,indivisibleparticles, calledatoms,whichareunchangeable. Atomsofoneparticularelementareallexactly alike,butatomsofdifferentelementsaredifferent. Atomsofelementscombinetoformmolecules ofacompoundformedthroughchemicalreactions inwhichatomsareneithercreatednordestroyed, JohnDalton(17661844) butareonlyrearranged. DaltonsmonographANewSystemofChemicalPhilosophywaspublishedin1808[1].Soonafter,atomic scienceprogressedinaverybigwaywhenFraunhoffer(1817),whilecarryingoutsometestsonthenew prisms he had made, reported dark lines in the spectra of stars [4]. He systematically catalogued his observations accurately. These dark or missing lines are called the Fraunhoffer lines. Fraunhoffer reported574missinglinesinthesolarspectrumandthisraisedafascinatingquestion:whywouldntthe sunemitjustthesecolors?Fraunhoffersexpertisewasonmakinglensesandprismsandopticaldevices ratherthanspectroscopy[5,6],andhedidnotreallyexplaintheoriginsofthemissingordarklines.In fact, it was the work of John Herschel and David Brewster which provided an interpretation of the Fraunhofferlineswhichtheyexplainedcouldeitherbecausedbyabsorptioninacoolgasintheearths upper atmosphere or in the stars outer atmosphere. Finally, the reversibility of the absorption and the emissionspectrumwasdemonstratedandexplainedbyKirchoffandBunsenin1860[7]. ThenineteenthcenturywitnessedobservationssuchastheDobereinerslawoftriadsandNewlands octaves which were the precursors of the tabular arrangement of the periodic properties of atoms, developedindependentlybyLotharMeyerandDmitriIvanovichMendeleev.Daltonsatomnowhad a firm place at the very base of the science of materials; the periodic properties of elements were connectedtoatomicweightsbyMendeleev[8].

II. DevelopmentofAtomicPhysicsasanEmpiricalScience: In the meanwhile, the Swedish spectroscopist Anders Jonas Angstrom (18141874) built high precision spectrometers and carried out accurate measurements [9] of wavelengths in the solar spectrum and reported over a hundred spectral lines. He was able to deduce from his spectra that hydrogen was present in the solar atmosphere. Angstroms pioneering work in precision spectroscopyisoneofthemostimportantdevelopmentsinourstoryoftheatom. ngstrm,AndersJns 181474,

SwedishPhysicist ngstrmsspectrometer

4101.2, 4340.1, 4860.74

and

6562.10

Angsrtomsmeasurementsonthespectrumofthehydrogenatom(1853) Angstrom measured with great precision the wavelengths of the visible lines in the emission spectrumofthehydrogenatom.Thefourvisiblelineshadwavelengthsof4101.2,4340.1,4860.74and 6562.10 , in units of length named after this skillful Swedish experimentalist. Even on the second look,veryfew,ifany,wouldrecognizeapatterninthesefournumbers,butJohanJacobBalmer,who was a teacher of Mathematics in a secondary school for girls figured out in 1884 that each of these fourwavelengthsconformtothefollowingmathematicalrelation: n2 = b 2 , n 4 withb=3645.6Angstromsandn=3,4,5,6.

 Balmersingeniousmindwentontopredictthattherewouldbeotherlinesinthespectrum,aswere indeed found later in the infrared part of the spectrum corresponding to n = 7, 8, etc., and he predictedalsothatthenumber4intheaboveformulacouldbereplacedbysquaresofotherintegers, 9,16,25,.etc. Sixyearslater,in1890,JohannesRobertRydberg(18541919)deducedindependently,without makinganyreferencetoBalmersformulathathewasunawareof,thatthefourspectrallinesinthe visiblepartofthehydrogenatomconformedtothefollowingrelation: 1 1 1 = RH 2 2 , n m whereinnandmareintegers,andRHisaconstant,nowknownastheRydbergsconstant,havinga valueof109,737cm1.BalmerandRydbergsworkepitomizesthegrandsuccessofprequantum mechanicsempiricalscience. II. DevelopmentofQuantumMechanics: Progress in the development of the empirical science of the atom overlapped with three major developmentsinPhysics: [i] thestruggles in theunderstanding of the spectral intensity distribution of radiationfrom a blackbody,intheworksofGustavKirchhoff(1859,1860),JosefStefan(1879),Ludwig Boltzmann(1884),WilhelmWien(1896)andMaxPlanck(1899)[10]. [ii]thediscovery(1887)ofthephotoelectriceffectintheworksofHeinrichHertzandPhilipp Lennard,anditsinterpretationbyAlbertEinstein(1905)[11]. [iii]thediscoveryofradioactivityandeventualrecognitionoftheparticleastheelectron[10]. Eachoftheabovethreedevelopmentsweretohaveahugeimpactonthedevelopmentofquantum mechanics and atomic physics which in fact took place hand in hand. The first of these arguably containedthegenesisofquantumtheoryinthecorpuscularhypothesismadebyPlanck.However, notwithstanding the success of his hypothesis, Planck was himself very weary of the corpuscular hypothesis he had made as an act of desperation to explain the black body radiation spectral intensitydistribution.ThomasKuhnthereforearguesthatitisnottoPlanckin1899buttoEinsteinin 1905, in his explanation of the HertzLennard experiment, that we owe the origins of quantum theory, for it was Einstein rather than Planck who placed the quantization of the electromagnetic radiation on firm logical footing [12]. The discovery of the electron, on the other hand, laid the foundationfortheRutherfordmodeloftheatom.WorkinginthelaboratoryofJ.J.Thomson,Ernest Rutherford, the First Baron of Nelson and Cambridge, carried out some of the most fascinating experiments that showed that theatomis mostly hollow, witha positive charge packedina rather denseandverytinyregionwhilemuchoftheemptyspacewasoccupiedbytheelectronsthatmade the atom neutral. Rutherfords model [13] of the atom was deduced from his experiments on the scatteringofalphaparticlesfromgold.ItwasagreatimprovementoverThomsonsjellymodel,and theimmediateprecursor[14]totheatomofNielsBohr(1913).

Thestabilityoftheatom,consideringthefactthatelectronsrevolvingaroundRutherfordsnucleus would radiate and loose energy, was explained away soon by the bold hypothesis made by Niels Bohr[15]whichenvisagedstationaryorbitstracedperiodicallybyelectronsalongtrajectorieswhich would quantize their angular momenta. The Bohr model found quick verifiability [16] in the experiment on electronatom collisions conducted by James Frank and Gustav Ludwig Hertz (nephewofHeinrichHertz). The RutherfordBohr model gave credibility to the BalmerRydberg expression for atomic spectral lines, but depended on intangible trajectories which required for their being the simultaneous knowledgeofbothpositionandmomentumoftheelectrons.Thiswasonethemostexcitingperiods inthedevelopmentofquantumtheorywhosestoryinterlacesintimatelywiththeunderstandingof the atom. The inaccessibility of the dynamically conjugate observables position and momentum for simultaneousaccuratemeasurementsplacedalowerlimitontheaccuracywithwhichthetwocould bemeasuredsimultaneously,andthisrecognitionlaidthefoundationofquantumtheoryenunciated in the celebrated uncertainty principle of Heisenberg. This principle negates the existence of orbits/trajectories. Banesh Hoffman describes in her book [17] RutherfordBohr orbits in a chapter titled the atom of Niels Bohr, but in the very next chapter in which she dispenses with the very notion of orbits/trajectories.Aptly,shehastitledthischapterastheatomofBohrkneels. Subsequent developments in quantum theory have no easy classical analogues. The formalism requiredreconciliationbetweentangibleobservationsandmathematicalabstractionsandthegrowth of the subject was entirely due to the passionate pursuits of intricate ideas by intellectual giants of that era. Intellectual giants debated consistencies and compatibilities [18], and quantum theory emerged triumphant in its ability to explain and predict physical observation. Throughout the development of the quantum theory, atomic physics remained at the focus. In fact, it was the systematic organization of the atomic spectral line intensities and the frequencies predicted by the RayleighRitzcombinationruleswhichledHeisenbergtodispensewiththeintangibleorbitsofNiels Bohr and develop a scheme that would address observables alone. The mathematical relationships thatemergedfromthisconsiderationledHeisenbergtothenowfamouscommutationrulesforthe positionandmomentumoperators[19]. Athispoint,ratherthangettingdrawndeeplyintothedevelopmentofquantumtheory,wereturnto developments directly in atomic physics. We consider the similarities between optical transitions givingrisetothealkaliatomspectrawhichareverysimilartothespectrumofthehydrogenatom. Consider the sodium atom for example with its 3s electron outside the neoncore making it very analogoustothetwobodyprotonelectronproblemofthehydrogenatom.Aninterestingvarianceis thefactthatwhiletheHatomenergyeigenstatesaredegeneratewithrespecttotheorbitalangular momentumquantumnumberl,suchisnotthecasefortheNaatom.Theclassicillustrationofthis fact is the appearance of the famous yellow line(s) of the sodium vapor lamp which result from electronictransitionsbetweenthe3pand3slevels.IntheHatom,thesestateswouldbedegenerate, and there would be no spectral transition between them. Now, there is a close connection between symmetryanddegeneracy;whenthesymmetryofaHamiltonianisloweredbyaperturbation(asin the Zeeman/Stark effect), the degeneracy is lifted (partially/wholly). This raises an interesting question: just what is the symmetry responsible for the degeneracy with respect to the l quantum numberinthecaseoftheHatomthatisbrokeninthecaseoftheNaatom?LaterworkbyVladimir Fock[20]providedthesubtleanswertothisbyexplainingthathydrogenwavefunctionspossessthe O(4) symmetry. The Fock Symmetry of the hydrogen atom explains the degeneracy of hydrogen

wavefunctions,andthisexplanationiseasilyoneofthemostimportantmilestonesinthefascinating sagaofatomicphysics.Theseissuescontinue[21]tomovethefrontiersofscience. Insomesense,thesymmetryresponsibleforthedegeneracywithrespecttothelquantumnumberis duetothedynamicalsymmetrylinkedtotheconstancyofthesocalledLaplaceRungeLenzvector. Thepotentialseenbyanelectroninthe3sstateofthesodiumatomwouldnotbestrictlygivenby inverselengthcausingtheBohrKeplerorbittoprecessandrequireanenergycorrectionassociated with the precessional motion. On the other hand, the notion of orbits being abandoned in formal quantum theory, the energy corrections are explained by analyzing analytical properties of the electron eigenfunctions when the electrons wavemechanics is determined by the electric field of a positive ion. This formalism is known as the quantum defect theory and it provides a common framework to deal with atomic bound states, series perturbations, autoionization states and also electronionscattering[22]. III. TheFourthQuantumNumberofAtomicElectrons: We now return to a further detail of the sodium yellow spectrum, the most prominent feature of which is the appearance of not one, but two lines, respectively of wavelengths 5896 and 5890 . These two spectral lines are respectively called the D1 and the D2 lines which originate due to splittingofthe3plevelsbyatiny0.0021eV.Weknownowthatthissplittingisduetowhatiscalled as the spinorbit interaction, but the understanding of the electrons spin was a huge challenge in developmentofphysics,notjustatomic. Wolfgang Pauli had proposed in order to explain the filling of the atomic shells according to the aufbauprinciplethattherehadtobeanadditionaldoublevaluedquantumnumber.Pauliconjectured thatinclusiveofthisnewquantumnumber,notwoelectronsinanatomcouldhavethesamesetof four quantum numbers. This inference is at the heart of what is called as the Pauli exclusion principle,butitdidnot,atthispointoftime[23],invoketheideaofspin.EvenasPaulisexclusion principle for the four quantum numbers was formulated in 1924, the idea of halfinteger spin quantumnumberitselfwouldneedtowaitforGeorgeUhlenbeckandSamuelGoudsmit! Uhlenbeck and Goudsmit were students of Ehrenfest and were struggling to understand the additional structure that was observed in the spectral lines of helium in the laboratory of Louis Paschen.Byplayingwiththenumbers,UhlenbeckandGoudsmitarrived[24]atthecorrectnumerical estimate of an additional angular momentum that an electron would have, but this would require halfintegral quantum numbers which was a very repugnant idea in the context of its time when physicistshad,afterall,reconciledwithintegralquantumnumbers!Amongstthosewhoviolently opposed the idea of halfinteger quantum numbers were some of the very founders of quantum mechanics,includingHeisenbergandSommerfeld,andevenPaulihimself! Therelationshipbetweenspinandstatisticscanbestatedverysimply:particleswithintegerspinsare describedbyBoseEinsteinstatistics,andthosewithhalfintegerspinsbyFermiDiracstatistics.This connectionisneverthelessverysubtle,andthecomplexitiesarebestdescribedbyFeynman[25]:It appearstobeoneofthefewplacesinphysicswherethereisarulewhichcanbestatedverysimply, but for which no one has found a simple and easy explanation. The explanation is down deep in relativisticquantummechanics.Thisprobablymeansthatwedonothaveacompleteunderstanding ofthefundamentalprinciplesinvolved.

The electron spin would subsequently find its formal place in quantum mechanics only in the relativistic formalism of Dirac [26, 27]. One of the very best sources to learn about spin is Tomonagasbook[28].ExperimentalcorrectnessoftheelectronspinisbestillustratedbytheStern Gerlachexperiment.

A memorial plaque honoring Otto Stern and Walther Gerlach, mounted in February 2002 near the entrance to thebuildinginFrankfurt,Germany[29]. Inscription translation: In February 1922 . . . was made the fundamental discovery of space quantization of the magnetic momentsofatoms.TheSternGerlachexperimentisthebasisof importantscientificandtechnologicaldevelopmentsinthe20th century, such as nuclear magnetic resonance, atomic clocks, or lasers.... Beforeweproceedtodiscussfurtherdetails,weremind,evenatthecostofpossibleredundancy,that thespinquantumnumberhasnothingtodowithspininthesenseofaspinningearth,inasmuch as the orbital angular momentum has nothing to do with orbit in the classical sense of an orbit/trajectorywhichwouldrequiresimultaneousknowledgeofbothpositionandmomentum.The hallmarkofquantummechanicsistheprincipleofuncertainty,whichlimitsthenumberandnature ofobservablesthataremeasurablesimultaneouslyandaccurately.Acompletesetofsuchquantities isthemostaphysicistexploresinordertogetthemaximuminformationaboutthequantumsystem. Whentheatomisplacedinamagneticfield,therelativestrengthsofthespinorbitinteractionand thecouplingoftheelectronsmagneticmomentwiththeexternalmagneticfielddeterminewhichset of four compatible measurements constitute the best set of good quantum labels. Exploration of atomicpropertiesbyusingexternalmagneticfieldsconstitutestherichfieldofZeemanPaschenBack spectroscopy.Likewise,Starkspectroscopyhasbecomearichprobeinwhichexternalelectricfields areemployedtoreducethesymmetryoftheatomicHamiltonianandliftdegeneracy. IV. TheManyElectronAtom: The manyelectron problem poses a completely new kind of difficulty: the problem can be posed formally,buttheconceptualizationoftheNelectronproblemleadstoimmediatedifficulties,asthe

solutiontotheNelectronSchrodingerequationrequiresthecorrespondingHamiltonian,whichitself requiresforitsconstructiontheverysamesolutions!Thiscanbereadilyseenfromthefollowingtwo relations:

H ( N ) ( N ) = E ( N ) ( N )

(N )

1 2 Z N 1 = i + 2 ri i < j =1 rij i =1
N

Onecancomeoutofthedilemma,followingatechniqueintroducedbyD.R.Hartree(18971958),by startingoutwithtrialwavefunctions,generatetheHamiltonianintermsofthesetrialfunctions,and then solve the problem numerically and iteratively till selfconsistency is reached. The Nelectron wavefunctions

( N ) areexpressedasanantisymmetrizedproductwrittenofteninadeterminantal
< ( N ) | H ( N ) | ( N ) >
while maintaining the individual electron

form, known as the Slater determinant. The process of getting such self consistent field (SCF) solutions is completely equivalent to a variational procedure that would seek to minimize the average value

wavefunctions in the antisymmetrized product orthogonal and normalized. The resulting SCF procedureisoftencalledastheHartreeFock(HF)method[30],whentwocomponentelectronspin wavefunctions are employed in the singleparticle states, or the DiracFock (DF) method [31] when fourcomponent relativistic bispinors are employed. D.R.Hartrees work was numerically intensive, and he was invited to the USA to advise on the development of the worlds first computer, the ENIAC, by John Eckert. However, Hartrees original numerical work was in the precomputer era, using mechanical differential analyzers he built, supported by his enthusiastic father William Hartree.

D.R.HartreeAlargedifferentialanalyzer, 18971958designedbyD.R.Hartreein1935

ThevariationalapproachemployedintheHF/DFmethodhowevermakesusewhatisknownasthe frozen orbital approximation. Essentially,it does not take into account the fact that if onewere to remove one of the Nelectrons from the system, the wavefunctions of the remaining N1 electrons

would, in some sense,relax. Within the frameworkof the frozen orbitalapproximation, the HF/DF equations connect the variational parameters of the SCF methodology to the binding energy of the atomic/molecular system. This result is known as the celebrated Koopmans theorem, after the solitary paper [32] Koopmans wrote in atomic physics before he switched over his attention to mathematicalproblemsinEconomics.Hewasevenawardedin1975theSverigesRiksbankPrizein EconomicSciencesinmemoryofAlfredNobel. For accurate estimates of atomic properties, it should now be clear to the reader that one must employ a relativistic model (such as the DiracFock) and also go beyond the frozen orbital approximation. The latter would give manyelectron wavefunctions that are superpositions of variousSlaterdeterminants,oneforeachpossibleconfigurationthatisworthyofconsideration.One is thus led to the MCHF (MultiConfigurational HartreeFock) or MCDF (MultiConfigurational DiracFock) schemes that represent this broad approach. If one were to look for exact analytical solutionsoftheNelectronatomic/molecularsystem,asG.E.Brownputit,havingnobodyatallis alreadytoomany[33].Onemustthereforemakeapproximations,andthechallengeinmanybody theory is to make the best and the most consistent approximation that one can. Powerful approximation methods such as the method of configuration interaction, MBPT (manybody perturbation theory) [34], diagrammatic perturbation theory [35], the relativistic random phase approximation(RRPA)[36],etc.aredevelopedforthispurpose,detailsofwhichgobeyondthescope ofthisoverview. V. AtomicPhysicsattheForefrontofFundamentalPhysics: The presence of electron spin, we have seen above, gives rise to the fine structure of the atomic energy levels. This constant is denoted by =e2/c and gets its name from the kind of splitting of atomic energy levels due to spinorbit interaction which give rise, for example, to the D1 and D2 lines of the sodium atomic spectrum as noted in Section III. Nevertheless, impacts physics in a multitudeofwaysandhasfascinatedphysicistseversinceitsdiscovery.SaidFeynman:Ithasbeena mysteryeversinceitwasdiscovered..andallgoodtheoreticalphysicistsputthisnumberupon theirwallandworryaboutit[37].Thefinestructureconstantscalesthestrengthoftheinteraction between a charged particle and the EM field. In the renormalization formalism of quantum field theory, the coupling strength is allowed to depend on the energyscale. This is often referred to as running of the coupling constant. Thus the constant perhaps changes. Laboratory high precision measurementscanbeperformedthatmaynotyieldanaccuratedeterminationofitself,butwould revealifthevaluedeterminedcouldinfactvarywithtime.Bystudyinghowlightwasabsorbedby metallicatomsingascloudsabout12billionlightyearsaway,theatomicastrophysicalspectroscopy research group of John Webb at University of New South Wales claimed that the structure of the atomsfromdistantquasarswouldhavebeenjustslightlydifferent,duetoadifferentvalueof[38]. On the other hand, more recent measurements [39] suggest that the value of the finestructure constantisnotchangingbymorethan1.6quadrillionthsof1percentperyear,withanuncertaintyof 2.3quadrillionthsof1percentperyear.Thefinestructureconstantcanbemeasuredbycarryingout different kinds of experiments which are just as challenging as much as the value of defies any simple theoretical prediction. There may be new physics that would throw up new questions if theoretical predictionsand accurate measurements of the fine structure constant fail to converge to the same value. Advances in atom interferometry have enabled the measurement of with a relativeuncertaintyof4.5x10 9[40].

Atomic physics is today contributing significantly to the relationships between symmetry and conservationlaws,pushingthefrontiersofphysicstotestthestandardmodelofphysicsand/orto explore physics beyond the standard model. As is well known, parity violating processes were admittedinPhysicsintheearlyworkduetoLeeandYang(1956)onweakinteractions(decay)and detected by Wu (1957). Following the electroweak unification in the GlashowWeinbergSalam model, search for parity nonconservation (PNC) in atomic processes began in the 1970s [41]. The gaugeBosonZ0ofthestandardmodel,unliketheWgaugeBosons,isneutralandwouldmediatean interaction between atomic electrons and the nucleus. The socalled nuclear weak charge QW is to Z0,whattheelectricchargeistotheCoulombinteraction.Theusualradiativetransitionsinatomic processes are governed by parity conserving selection rules imposed by the electromagnetic Hamiltonain. The electroweak Hamiltonian, however, does not commute with the parity operator and enables detection of parityviolating atomic transitions. In fact, there are two sources of parity nonconservation (PNC) in atoms: (1) the electronnucleus weak interaction and (2) the interaction (sometimescalledasPNChyperfineinteraction)ofelectronswiththenuclearanapolemoment.PNC effectinatomiccesiumyieldsthevalueofQW(133Cs)72.90,notinunreasonabledisagreementwith the value of QW(133Cs) 73.09 obtained from highenergy experiments extrapolated to atomic scale [42].Asignificantlylargevalueoftheanapolemomentofthenucleonhasbeenestimatedinthecase ofcesium,augmentedbycollectivenucleareffects.ThediscoveryofCPviolationinthedecayofK mesonspromptedthesearchforviolationofthetimereversalsymmetry.ViolationofTsymmetry would require an elementary particle, atom or molecule to possess a permanent electric dipole moment(EDM),whichisexpectedtobeenhancedinheavyatom/molecule.Thestandardmodelof particle physics predicts dipole moments that would be too tiny to be observable at all. EDM measurements therefore provide fascinating tests to explore new physics beyond the standard model. Reliable accurate measurements in agreement with predictions of a robust theoretical formulationhasthepotentialoftellingusifandwhatphysicsistherebeyondthestandardmodel, sincelimitsonEDMswouldputconditionsonsupersymmetricgaugetheories[43,44]. Thisfragmentarytalehashadtonotonlyskipsomeveryexcitingdevelopments,butalsohastohop backandforthintimetopickuppiecescrucialtothisvariegatedtheme.

10

Diracs relativistic hydrogen atom LambHyperfine givesstateswithdifferentlbuthaving ShiftStructure samen&samejtobedegenerate. WillisE.Lamb (19132008) NobelPrize(1955)

One of the very important consequences of Diracs relativistic solution to the quantum hydrogen atom problem is that the energy levels depend on the (n,j) quantum number; it gives degenerate solutionsfordifferentvaluesofl.Thisturnsouttobeonlyapproximatelycorrect,foritignores,as explained by Bethe, the quantization of the electromagnetic field and the correction to this was observed in the beautiful experiment carried out by W.E.Lamb and R.C.Retherford in 1947. The inclusion of this effect manifests as an energy shift, called the Lamb Shift between the 2S1/2(n=2,l=0,j=1/2) and 2P1/2(n=2,l=1,j=1/2) levels. Corrections that result in the Lamb shift are about 10% of the finestructure for the l=0 states (and much smaller for larger l). These terms are best expressedusingFeynmandiagramsforvacuumpolarization,electronmassrenormalization,etc.of quantum electrodynamics (QED). The contributors to QED, Dyson, Feynman, Schwinger and Tomonaga,were men ofexceptional brilliance [45]. The magnetic moment ofprotons andneutrons comesfromthequarksandthegluonsandallthisaddsuptoprovideanetspinmagneticmomentto the nucleus which interacts with the electrons magnetic moment to generate what is called as the hyperfinestructure.Highprecisionhyperfinestructurestudiesprovidesanextremelyvaluabletool inprovidingstringenttestsonthequalityofatomicwavefunctions,sinceitcanusuallybemeasured veryaccurately,andthenuclearmagneticmomentcanbedeterminedindependently. VI. AtomicPhysicsattheFrontierofTechnology: The radiation pressure that turns a comets tail away from the sun has extremely fascinating applications in laboratory atomic physics and is at the very root of the entire discipline of laser coolingandtrapping.Atomsand/ormoleculesatroomtemperaturemoveatabout300m/s,whichis close to the speed of sound. To do precision spectroscopy of atoms and to develop atomic clocks, atoms must be slowed down. What one exploits to achieve this is the electromagnetic radiation pressure exerted on the atoms. The resulting interactions are broadly, in this context, classified as scattering force and a dipole force. The former results in scattering of the incident radiation in random directions and the latter induce a dipole moment in the atom which interacts with the

11

gradientoftheincidentelectromagneticfield.Thecoolingandtrappingofatomsisanextraordinary phenomenonwhichisachievedbytheseprocessesandinvestigatedfurtherbytechniquessuchasthe high precision magnetooptical trap recoilion momentum spectroscopy. Further evaporative cooling techniques are employed to achieve temperatures that are cold enough to attain Bose Einsteincondensation.Thisisanunsualstateofmattersincealltheatomsofthesystemcoalesceinto a quantum state in which their individual identity is overtaken by a condensed state of the many atom system in which each has the same state and the same phase. Such a state was predicted by BoseandEinsteinintheirjointpublicationof1922,andachievedforthefirsttimeinalaboratoryin 1995 by E.A. Cornell and C.E. Wieman. Developments in laser techniques and associated quantum opticshaveledtothefollowingNobelprizesinthefieldofatomicphysicsinrecentyears: 1)Forthedevelopmentofmethodstocoolandtrapatomswithlaserlight[StevenChu,; ClaudeN.CohenTannoudji;WilliamD.Phillips,1997], 2)ForachievingtheBoseEinsteincondensationinalkaliatoms[E.A.Cornell,C.E.Wieman, WolfgangKetterle,2002]and 3)Forprecisionlaserspectroscopicmeasurementsandquantumoptics[JohnL.Hall,; TheodorW.Hnsch,;RoyGlauber,2005]. Lasercoolingandtrappingofatomshasledtomanyfascinatingapplications,sincewhenanobject bends light, the momentum of light changes, and to conserve momentum, the momentum of the objectitselfmustundergoanoppositechange(conservationofmomentum)effectively,itislikea forceactingontheobject.Onecanthususelighttomanipulatemicroscopicobjectsassmallassingle atoms[46]. Using laser cooling techniques, one can not only tweeze and manipulate tiny objects of atomic dimensions,butalsoachievestremendousenhancementintheaccuracyofatomicclocks. A modern atomic mercury ion clock [48] which measuresopticalfrequencyofasingleioninanultra cold electromagnetic trap is now developed that provides extremely accurate determination of time standard.Thisclockwouldnotgainorloseevenone secondin400millionyears! Measurements of optical frequencies with such amazing accuracy is enabled by advances leading to the femtosecond laser frequency comb and very narrowlinewidthlasers.Theatomicmercuryclockis about five times more accurate than the cesium fountain clock. Improved accuracy in time Thefirstcesiumatomicbeamclockas measurement is continuously sought since it is of portrayedbyRipleysBelieveItorNotin tremendous consequence navigation, global September1953. positioning systems, deepspace communication, etc. (1999RipleyEntertainmentInc.) Besides, highly accurate measurement of time is required to investigate if the fundamental constants TakenfromAtomicClocksMeetLaser of nature vary over long periods through which the Cooling[47] universeevolves.

12

Other quantum controls on positioning single atoms have led to extraordinary advances in nanotechnology.TheseareinspiredbythequestionRichardFeynmanaskedinhisfamoustalkThere isPlentyofRoomattheBottomgivenatCaltechin1959:Whatwouldhappen,Feynmanasked,if wecouldarrangetheatomsonebyonethewaywewantthem?. A3sp3statepointstowardsthesurfacenormalontheSi(111) surface,andtheimageofthisatomshouldbesymmetricwith respecttothezaxis.

Electron excited into a Because images in AFM are a convolution of tip and sample superposition of 2500 angular states, and the sample state is well known in this case, the tip momentum states for n = 50 stateismostlikelytobetwo3sp3statesoriginatinginasingleSi Rydberg manifold in H atom tipatom[50]. [51]. AteamofscientistsatOsaka,forexample,usedthetipofanatomicforcemicroscopetoliftasingle atom from a surface and then replace it [49]. This approach brings within reach assembling nano gadgetsbybringingtogetheratomsonebyone! OnecanexciteanelectroninanatomselectivelybyusingUVlaserpulsesandlowerfrequency electromagneticwavestoahighlyexcitedRydbergstateandscoopouttheelectrondensity distributionsoastoleaveadesiredpattern,suchaswouldgeneratethewordOPTICS[50].The amountofinformationthatcanthusbestoredinasingleatomisincredible!Besides,Rydbergatoms arepotentialcandidatesformakingaquantumcomputer[52].Furthermore,ithasbeenfoundvery recently[53]thathighlyexcited(n=72)canbeproducedbylinearlypolarizedlightatmicrowave frequencyshoneonLiatomtofirstlocktheelectronmotionintoanapproximatesemiclassicalorbit. Bysubsequentcontrolofthepolarizationstateoftheappliedmicrowavefield,specificallyby changingittocircularpolarizationsomewhatslowlycomparedtoorbitalfrequency,themotionof theelectronisthendescribableintermsofanondispersiveBohrwavepacket.Thishasbeenhailed asasuperbdemonstrationofBohrscorrespondenceprinciple[54]anddescribedasanatomic analogueofthemotionoftheclassicalfiveLagrangepointsofthesunearthsystem,withtheearths effectreplacedbythatofthecircularlypolarizedmicrowavefield. We conclude by highlighting the fact that Daltons atomistic model laid seminal foundation for the scientific, analytical approach to investigate condensed matter. In fact, even as we know now that the atomhascognizablepartsinconflictwithDaltonsfirstpostulate,itistheveryatomisticapproachwhich continues to provide insight into deepseated fundamental laws of nature which reveal themselves through the discovery and predictions of elementary particles inclusive of those which mediate interactionsbetweenthem.ItisnotsurprisingthentounderstandwhyRichardFeynman[55]said:If,in somecataclysm,allofscientificknowledgeweretobedestroyed,andonlyonesentencepassedontothe nextgenerationsofcreatures,whatstatementwouldcontainthemostinformationinthefewestwords?I

13

believeitistheatomichypothesis(ortheatomicfactorwhateveryouwishtocallit)thatallthingsare madeofatomslittleparticlesthatmovearoundinperpetualmotion,attractingeachotherwhentheyare alittledistanceapart,butrepellinguponbeingsqueezedintooneanother. Thistaleis,asthetitleconfesses,anessentiallyfragmentaryone.Verymanyimportantdevelopmentsare omitted.Thefieldisvast,butevenanarrowviewofitseemstobeanexcitingone!Therewouldbemany alternativeviewsofthedevelopmentsinthefield,evennonoverlapping,thatmustbeintegratedtogeta completepicturewhichisdismallybeyondthescopeofthepresentattempt. References: [1] JohnDalton(1808,1810,1827)ANewSystemofChemicalPhilosophy S.Russell,Manchester(England) [2] AaronJohnIhde(1984)TheDevelopmentofModernChemistry(Dover) [3] H.CarringtonBolton(1895)JohnDaltonandtheRiseofModernChemistry J.Am.Chem.Soc.,1895,17(8),p658 [4] Fraunhoffer,J.:1817,DenkschriftenderMch.AkademiederWissenchaften.5,193. [5] MylesW.Jackson(1996)inScientificCredibilityandTechnicalStandardsin 19thandEarly20thCenturyGermanyandBritainEd.JedZ.Buchwald(Springer) [6] MylesW.Jackson(2000)SpectrumofBelief:JosephVonFraunhoferandthe CraftofPrecisionOptics(MITPress) [7] GustavKirchhoffandRobertBunsen(1860)ChemicalAnalysisbyObservationofSpectra AnnalenderPhysikundderChemie(Poggendorff),Vol.110,pp.161189(Heidelberg) [8] DmitriiMendeleev(1869)OntheRelationshipofthePropertiesoftheElementstotheirAtomic WeightsZhurnalRusskoeFizikoKhimicheskoeObshchestvo1,6077;abstractedin ZeitschriftfrChemie12,405406(1869). [9] AndersJonasngstrm(1868)Recherchessurlespectresolaire [10] F.KRichtmyer,E.HKennard,T.Lauristen(1955)IntroductiontoModernPhysics(5thedition ed.).NewYork:McGrawHillBookCompany [11] PranawaC.DeshmukhandShyamalaVenkataraman(2006)100YearsofEinsteins PhotoelectricEffect,BulletinofIndianPhysicsTeachersAssociation,publishedin twoparts:September&OctoberIssuesof2006. [12] ThomasKuhn(1987)BlackBodyTheoryandtheQuantumDiscontinuity,18941912University ofChicagoPress,Chicago) [13] Rutherford,E.(1911)TheScatteringof and ParticlesbyMatterandtheStructureofthe AtomPhil.Mag.21(1911)669 [14] Heilbron,J.L.(1981)HistoricalStudiesintheTheoryofAtomicStructureAyerPublishing [15] Bohr,N.(1913)PhilosophicalMagazine26,125 [16] FranckJandHertzG(1914)Verh.DeutschePhys.Ges.16457 [17] BaneshHoffman(1959)`TheStrangeStoryoftheQuantum(GeneralPublishing Co.Ltd.,Toronto) [18] Sachs,M.(1988)EinsteinversusBohr(OpenCourtPublishingCo.) [19] JeremyBernsteina(2005)MaxBornandthequantumtheoryAm.J.Phys.7311,November [20] Fock,V.A.(1935)Z.Phys.98145 [21] AVMeremianinandJMRost(2006)MultipoleexpansionsandFocksymmetryofthehydrogen atomJ.Phys.A:Math.Gen.391242712445 [22] Seaton,M.J.(1983)QuantumDefectTheoryRep.Prog.Phys.46167 [23] Pauli,W.(1925)Z.Physik32794. [24] Uhlenbeck,G.E.andGoudsmit,S(1926)Naturwissenschaften47(1925)953.

14

[25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38]

[39]

[40]

[41] [42] [43] [44] [45] [46]

Feynman,RichardFeynmanLecturesVol.III,page43 Dirac,P.A.M.(1928)Thequantumtheoryoftheelectron Proc.R.Soc.(London)A117610612 Dirac,P.A.M.(1928)ThequantumtheoryoftheelectronPartII Proc.R.Soc.(London)A118351361 Tomonaga,SinItiro(1997)TheTheoryofSpin TranslatedinEnglishbyTakeshiOka(TheUniv.ofChicagoPress) Friedrich,BretislavandHerschbach,Dudley,(2003)SternandGerlach:HowaBadCigar HelpedReorientAtomicPhysicsPhysicsToday,December2003 Bethe,H.A.andJackiw(1986)IntermediateQuantumMechanics3rded.MenloPark,CA: Benjamin/Cummings. Grant,I.P.(1970)Adv.Phys.,19,747. Koopmans,T.C.(1934)`UeberdieZuordaungvonWellenfunktionenundEigenwertenzuden einzelnenElektroneneinesAtoms,Physica1,no.2,pp.104113. Mattuck,RichardD.(1992)AGuidetoFeynmanDiagramsintheManybodyProblem,Edition: 2,illustratedPublishedbyCourierDoverPublications Kelly,H.P.(1964)ManyBodyPerturbationTheoryAppliedtoAtoms, Phys.Rev.136,B896B912(1964) Raimes,S.(1972)ManyElectronTheoryAmsterdamLondon,NorthHollandPublishing Company. Johnson,W.R.andLin,C.D.(1979)Multichannelrelativisticrandomphaseapproximationforthe photoionizationofatomsPhys.Rev.A20,964977 HelgeKragh(2003)MagicNumber:Apartialhistoryofthefinestructureconstant Arch.Hist.Eaxct.Sci.Vol.57page395431 JohnK.Webb,MichaelT.Murphy,VictorV.FlambaumandStephenJ.Curran(2003)Does thefinestructureconstantvary?Athirdquasarabsorptionsampleconsistentwithvarying AstrophysicsandSpaceScience283:4565575 T.Rosenband,D.B.Hume,P.O.Schmidt,C.W.Chou,A.Brusch,L.Lorini,W.H.Oskay,R.E. Drullinger,T.M.Fortier,J.E.Stalnaker,S.A.Diddams,W.C.Swann,N.R.Newbury,W.M. Itano,D.J.Wineland,andJ.C.Bergquist(2008)FrequencyratioofAl+andHg+singleionoptical clocks;metrologyatthe17thdecimalplace Science,Vol.319.no.5871,pp.18081812. M.Cadoret,E.DeMirandes,P.Clade,C.Schwob,F.Nez,L.JulienandF.BirabenandS. GuellatiKhelifa(2008)Determinationofthefinestructureconstantwithatominterferometryand Blochoscillationshttp://hal.archivesouvertes.fr/hal00347833/fr/ Budker,D.,Kimball,D.F.,DeMille,D.P.,(2004)AtomicPhysics:AnExplorationThrough ProblemsandSolutions(Oxford) Khriplovich,I.B.(2004)FundamentalSymmetriesandAtomicPhysics PhysicaScriptaT1125262 Hasty,R.etal.(2000)StrangeMagnetismandtheAnapoleStructureoftheProton ScienceVol.29015 Hudson, J.J., Sauer, B.E., Tarbutt, M.R. and Hinds, E.A. (2002)Measurementoftheelectron electricdipolemomentusingYbFmoleculeshttp://arxiv.org/abs/hepex/0202014v2 SilvanS.Schweber(1994)QEDandtheMenwhoMadeit:Dyson,Feynman,Schwinger,and Tomonaga,PrincetonUniversityPress. Zhao,Y,Zhai,W.C.,Seah,W.L.,Lim,K.Y.,Cheong,F.C.,Sow,C.H.(2007)Scanningmirror onavibratingmembranefordynamicopticaltrappingAppliedPhys.B86p.243248

15

[47]

[48]

[49]

[50] [51] [52] [53] [54] [55]

WalterF.BuellandBernardoJaduszliwerAtomicClocksMeetLaserCooling http://www.aero.org/publications/crosslink/winter2000/02.html (Downloadedon05/03/09at11:55am) Oskay,W.H.,Diddams,S.A.,Donley,E.A.,Fortier,T.M.,Heavner,T.P.,Hollberg,L.,Itano, W.M.,Jefferts,S.R.,Delaney,M.J.,Kim,K.,Levi,F.,Parker,T.E.andBergquist,J.C.(2006) SingleAtomOpticalClockwithHighAccuracyPhys.Rev.Lett.97,020801 NoriakiOyabu,scarCustance,InsookYi,YasuhiroSugawaraandSeizoMorita(2003) Mechanical vertical manipulation of selected single atoms by soft nanoindentation using near contact atomic force microscopy,Phys.Rev.Lett.90,176102 FranzJ.Giessibl(2003)Advancesinatomicforcemicroscopy http://arxiv.org/abs/condmat/0305119v1 CarlosStroudandMichaelNoel(1999)OpticsandPhotonicsNews; http://www.aip.org/png/html/Optatom.htm IgorIRyabtsev,DenisBTretyakovandIlyaIBeterov(2005)ApplicabilityofRydbergatoms toquantumcomputersJ.Phys.B:At.Mol.Opt.Phys.38S421S436 Maeda,H.,Gurian,J.H.,andGallagher,T.F.(2009)Phys.Rev.Lett.102,103001 Stroud,C.R.(Jr.)(2009)AnastronomicalsolutiontoanoldquantumproblemPhysics219 FeynmanRP,LeightonRBandSandsM(1968)TheFeynmanLecturesonPhysics, (NY:AddisonWesley)Vol1,Sec12.

This article is partly based on the Keynote Address given by PCD at the Topical Conference on Atomic and Molecular Physics (TC2008) held at Sardar Patel University, Vallabh Vidyanagar (Gujarat), January 3-5, 2008.

16