Molecular Electronics: Some Views on Transport Junctions and beyond Author(s): Christian Joachim and Mark A.

Ratner Source: Proceedings of the National Academy of Sciences of the United States of America, Vol. 102, No. 25 (Jun. 21, 2005), pp. 8801-8808 Published by: National Academy of Sciences Stable URL: http://www.jstor.org/stable/3375617 Accessed: 25/06/2010 13:16
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-i

Molecular beyond and

electronics:

Some

views

on

transport

junctions
2

Joachim* and MarkA Ratnertt Christian

Structurales,Centre National de la Recherche Scientifique, Z9, GroupeNanoSciences, Centre d'Elaborationde Materiaux et d'Etudes of Chemistry,Northwestern University,2145 Jeanne Marvig, BP 94347, 31055 Tou/ouse Cedex 4, France;and tDepartment Rue Road, Evanston, IL60208-3113 Sheridan
Ratner, January 19, 2005 by Contributed Mark AW

cE

responseof moleeulesas partsof a the set a comprises fundamental of ssues concerning electronlc eleetronlcs field The of molecular of aspec1:s these subfields.The most important We area and strueture a technologyWfaeing of seienceZ will overviewsome unitsarxd broadlybased on usingthe mesoseopic are logicor memory as individual ideas advanced in the field involvethe use of molecules junetiontransportwhere usuallyaddressesmolecular eleetronlcs work in molesular Current state quantum spaee of the moler:ule. generalas idea Landauer of "eonduction se:attering8' filndamentai Thisis the electrons: for moleeuleacts as a barrier incoming the for a guidingmechanism (oherenteleeas Anotherpoint of vlew in termsof superexchange junctionstrustures. to ized molecular coupilng Thelast seew strongwibronic relatively throlighthe moleular bridgeis disoussedMoletulesgenerallyexhibit spectroseopyR transfer tron hysteresisInjunctioncharge inelasticelectrontunneling effeets, including of tion this overviewfocuses on wibronie junctions. transport resistaneeInmolecular and negativedifferential transportt or device logic and local leads (33, 34). mightopen. These new schemes schemes .e a smglemo ecu. or an How from simpleend groups,suchas Aside requireextensivemodelingstudiesto will orderednetworkof molecules addingall of these lateralgroupsis thiols, architecture, amonga semiclassical select (1-7) can performtransport procedure for problematic the deposition the forcing moleculeto behavelike a using (8, 9) or a computation and sublimation, self-assembly), (solubility, (23), a quasielectroniccircuit traditional (10), mechanical magnetic(11), or elecThe techniques. new requiring deposition electronicinterone quantum employing (12) tronic degreesof freedomis becomfaciliweightof these molecular molecular or effects (24) or a Hamiltonian ference afterthe an ing activefield of research, may tators be largerthanthe boarditself. architecture, computing-like quantum ideas of the 1970s(13, 14). suggestive first workon nanofabThereis little current dyquantum the where intramolecular molecular Useof electronicand nuclear with and rication nanopackaging atomic moleculedefinesa compuof namics the of degrees freedomto createa device self Molecular assembly precision. scale scheme(25). tation embeddedinsidea uniquemolefunction such permitmoleculesto self-build should data, permitting For interconnects majorchallengein the applicais cule a junctions(35, as structures interconnect betweena and charge, energyexchanges ideas (15, electronics tionof molecular an 36).It is fairto anticipate explosionof world moleculeand the external single wouldbe functionality Single 16).Its ultimate aimedat suchfabrication. activities prob(theso-callednanocommunication resources by realized usingthe physical devicesor logic gateswill have molecular to createan is a inside singlemoleculeto integratea full lem),one majorchallenge in whichthe fromthe labto tobe packaged transition clean technology atomically and/or logic unit (17). arithmetic to oratory the market. precisionand the positioning fabrication entailsa seriesof electronics elecMolecular molecular Morefundamentally, of a singleatom,molecule,or atomicwire and experimental, modeling conceptual, to workis contributing the knowltronics as dis(1-7, 18-20). Those challenges on a surfaceis betterthan0.1 nm, (27), edgeand capability and challenges base of molecular of the architecture molecules,the cussedby the Gourdon(26), Hersam concern matterscience.In this contricondensed andHo (28) groupsin this issue of PNAS. the and, interconnects moregenerally, we bution, focusnot on elastictransport is positioning a Atomicscale precision schemeswithinand nanocommunication whichhas been junctions, in molecular accompaveryactivenew field of research and amongmolecules,the chemistry, reviewed(7-9, 19). Rather,we recently shiftfrommetallic natureof charge (froma more appliedpoint of view) nano- nied by a progressive examinethe fundamental surfacesto interconto semiconducting techniques. and whereinthe mofabrication nanopackaging in suchsystems transport moleculeto a a the In architecture, mainchallengeis to nect very precisely single lecularentityacts as a guide/filterfor lead (29, 30). macroscopic Mechvwhethera moleculecan prodetermine Superexchange chargeflow. In Thve maynot The mainchemicalchallenge a vide an interconnect, switch,a transistor nism,we showthatnew waysof undermolecular of be the synthesis a conjugated (13, 14, 21) or a morecomplexfunction, the standing physicsof signalexchange to "board" performelectronicdevice a full arithwire can enlarge suchas a logicgate or even a through long molecular even act as a digitallogic or functions by meticand logic unit (17, 92). If the ultielectronics addingthe lanmolecular challengerecomscale information mate miniaturization of an electronic gate.A majorchemistry guageof the quantum the such quiresequipping boardwith lateral can is one moleculeper transistor, device munity.This discussion be generalized to groups,not contributing the chemical to electronictechnology wiresinterconnected molecular hybrid frommolecular the but functiondirectly protecting molec- n = 2 electrodes a largermoleculewith whatis expectedfor futo mightapproach and Sub- ularelectronicfunctionality assemnanoelectronics. links. turesemiconductor N interfacial the blingand stabilizing moleculeon a has in this direction stantialprogress One exampleinvolves by since 1974,as exemplified the givensubstrate. occurred inelasticelectron to chemistry maintainthe molecular ET, Abbreviations: electrontransfer;IETS, et al. (22) in this from Ebling contribution tunneling spectroscopy;NDR,negative differential resisboardawayfromthe surfacewhilefaciliSpecialFeaturedealingwith molecular sin- tance. microscope tunneling tatingscanning if Goingfurther, there are rectification. (31, manipulation 32). Other tTo whom correspondenceshould be addressed. E-mail: gle molecule in resources a single enoughquantum ratnerEchem.northwestern.edu. groupsmustprovidea good chemical moleculeto integratemore thanone debetweenthe molecular O 2005 by The NationalAcademyof Sciencesof the USA electroniccoupling vice function,then new computational
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www.pnas.org/cgi/doi/10.

l 073/pnas.0500075102

PNAS | June 21, 2005

| volS 102 | noN25 | 8801-8808

The Superexchange Mechanism

an Consider isolated,zero-temperature part moleculemade of a longitudinal (L) group(M1) at one end with a substituent of L and anothergroup(M2) at the other in prepared a end of L. Wheninitially state M1--L-M2, nonstationary quantum this moleculeshouldideallyoscillateback andforthbetweenthe formsM1--SM2 and M1-L-M2-. These time-dependent are oscillations the sigHeisenberg-Rabi superexchange natureof a purequantum effect (37, 38), whichwill then dephase, untilthe M1-L-M2moleculehas relaxed into a (M1-L-M2)- state.Thisbasic is phenomenon at the originof quantum nearlyall of the proposedand/or experideviceor electronics mentedmolecular logicfunctions. reflects mechanism The superexchange wire L in inthe role of the molecular the creasing effectiveelectroniccoupling states betweenthe two quantum V12 M1--M2 and M1-M2- when M1 and M2 very far apart.In the coare maintained herentregime,the effect of the bridgeL material is not the creationof a classical channelfor the chargeto be transferred from M1 to M2 by usingstationsalongL by tunneling (39). Rather,L facilitates state space the increasing size of quantum d(t) trajectory (40, 41) for the quantum evolutionof the describing quantum M1--IM2 to reachthe vicinityof the M1-L-M2-, as targetstate representing to trajectory to compared the quantum from M1--M2. reachM1-M2- starting d(t) an Optimizing average to pass in to close proximity M1-L-M2- starting the from M1--L-M2 or minimizing distancebetweend(t) and M1-L-M2- for a congivenvalueof t is a difficultquantum trolproblem.Usually,it is reducedto electrontransfer the optimizing WtranSfer (ET) ratebetweenM1--L-M2 and M1-L-M2- (39). The electroniccomis simplythe secular ponentof WtranSfer nearly of frequency the Heisenberg-Rabi betweenthe M1-periodicoscillations L-M2 and the M1-L-M2- states.It dewith an injectiongap pends(for situations far exceedingthermalenergy)exponentiallyon the lengthof the ligandL, on and its conformation, on the detailed of properties the virtualelectronicstates enteringthe ET process(39, 42). Those controlthe extensionand quality variables quantum of d(t) on the corresponding state space.Reducingthe d(t) characterisis tics to only WtrSfer a drasticreduction on properties the ligand of the quantum L. For example,the time for an electron to oscillatebetweenM1 and M2 through polyeneligandin S-nm-long a hypothetical metal complexis about1 ps a binuclear (40, 41). This time can be comparedto the 0.1 fs takenby a ballisticelectronto
8802 | www.pnas.org/cgi/doi/

sA

L,#3
Fig. 1. A molecularwire Ladsorbed and providingelectronic coupling between two metallic clustersA processguided by Lbetween the state A--L-B and B.Injectingone electron on A = (M1)nwill trigger an ET Thisprocesscan be followed in time by usingthe electron detector N(t)before and A-L-B- with B = (M2)n. it stops because of decoherence and relaxationeffects at the interface,on the molecule, and in the A and B clusters.

metallic run over S nm of a mesoscopic forfrom the Landauer wire (estimated mula,underbias V of 1 V, or from the Fermivelocityin copper).Using only to optimized(t) maynot be Wtransfer the enoughto understand largedifference betweenthe two processes. By selectinga metallicatom and bondthe ing patternand extending lateralsize of M1 and M2, one can use the superexto changeinteraction couple two metallic (Fig. 1). In this case, padselectronically the (Ml)n-L4M2)nelectroniccoupling will dependalso on a new size parameter n, noo for the metal-L-metaltunnel junctioncase. As for n = 1, addingone electronto (Ml)n will triggera superexprocessfor the change,time-dependent by to electronto be transferred (M2)n the of ligand.The d(t) trajectory molecular more complex this processis certainly thanfor n = 1 andwill dependon the electronicdensityof statesof A = (Ml)n the and B = (M2)n.As a consequence, betweenthe electroniccouplingV12(n) and (Ml)n--L-(M2)n the (Ml)n-b(M2)n statesis a functionof n, and the corrediffers rate WreSerVojr transfer sponding Measuring from WtranSfer substantially for V12(n) very largen is possibleby using as experiments, already microwave-type superconductor with mesoscopic practiced in qubits(43). The discussion this section modifiedby vibronicand is dramatically in processesas discussed Decodephasing
herence and Relaxation (InelasticEfJects)

electroniccurrent dure,the maximum in intensitymeasured the externalcircuit

. . .

1S SlMply:

Itransf=

ed(y(t))/dt

4eWreservoir

[1]

by and in the contribution Ness and Fisher.

Source and Detection of Tunneling Electron

of interpretation physical One heuristic regime,basedon ref. 44, the tunneling Supapproach. involvesa shot-noise-like pose now that each time a singleET eventoccursbetweenclusterA and clussystempreter B in the A-1AB quantum electronis sentedin Fig. 1, the transferred anremovedfrom B and,immediately, otherelectronis providedto the cluster quana A, againpreparing nonstationary tum state A--bB. Followingthis proce-

with N the numberoperatormeasured on the right pad. gedankenexperiThe corresponding in mentalset up is presented Fig. 2. As in Fig. 1, the set up includesa detectorof singleET eventsable to followin time the of N(t) electronpopulation clusterB. A sourceS is now actingin synchronization with the ET events.The current(I) is calthe culatedby performing time averageof signalmeasured the N(t) time-dependent at the detector.The idealN(t) shapeis a arcs.The in succession time of sinusoidal to rise of each arccorresponds the growth of of the electronicpopulation clusterB in time, due to ET. Whenthis population the its approaches maximum, electronis pumpedout of clusterB. The maximum is possiblecurrent obtainedby supposing that the sourceS is ideallysynchronized with the ET events.This circumstance leads to a periodicN(t) signalwith no betweeneach period.In this interruption case, the currentintensitydependsonly which on the ET rate WreservOirX is calcuin latedby averaging time the idealN(t) signalshapegivenin Fig. 3. Of course, an ideal synchronized source S as describedin Fig. 2 is not known.A source of voltage V is usually used to form a closed electricalcircuit deliveringelectronsto the A-L-B molecularjunction.In this case, the maximum tunnelingcurrentis given by the Landauer formula(45):
8he 2V, = IScat ( WreServoir2/x2) 12]

whereX is the lead electronicconduction and bandwidth V is the biasvoltageof the A-LB tunneljunction.This currentis by that the maximum can be measured for amperometer a given the macroscopic A-bB junction.For example,a sufficient
Joachim and Ratner

10.1073/pnas.0500075102

4E,
Fig.2. A source S is added to Fig. 1, ideally synchronizedwith each ETevent from A to Bthrough L.An ideal S is supposed to provide an electron at clusterA each time the previousone had been pumped out of cluster B. A macroscopicamperometer is added to measure the tunnel currentdensity in the circuit.

will increaseof the lead ohmicresistance transform voltagesourceto the effectively is source.If this lead resistance a current of muchhigherthanthe quantum resistanceh/2e2, no electronswill be provided to the A-L-B junction.The sourcewill be blockedby the so-calledCoulombblockade effect (46). Deliveryof electronsto wire throughthe molecular be transferred is a very delicateprocesswhose time dependencewill not followthe N(t) ideal time sequence(Fig. 3). Whereasdeliveryof electronsto the wire is a classical-quantum molecular process,the detectionof the conversion throughthe afterits transfer electrons wire is a very peculiarquanmolecular process,as measurement tum-classical by can be demonstrated usingthe Ehrenthat fest theorem,indicating the current valuegivenby (Eq. 2) resultsfromthe obof measurement a specificquantum in servable the tunneljunction(47). It can be shownthat this intensityis givenby the averageoverjunctionscattering quantum [N(t)/2, of eigenstates the commutator HamilH1,whereH is the single-electron tonianof the A-bB tunneljunction. Both the sourceof tunnelingelectrons electrons and detectionof the transferred tunneling current to obtaina measurable have amperometer at the macroscopic been studiedvery little,eitherexperimentallyor theoretically.

N(t)h 2e_ e

tJ

'

Fig. 3. The ideal N(t) time-dependent electron population on cluster Bwhen the source S in Fig.2 is synchronizedwith each ETevent. As indicated, each arcissupposed to be normalizedto effectively one ETat a time. T is the full duration of the event before its fast pumping out of cluster B, X =
h/4Va2(n).

of One indication the poor performanceof the actualvoltagegeneratorcapacitance lead-stray interconnection between tunnelsourcesis the difference givenby Eqs. 1 and 2. For a the intensity molecular wire with an shortconjugated beeffectiveelectroniccouplingV12(n) tween the two electrodesof 10 meV (1 eV = 1.602 x 10-19J), the maximum is current 1.5 ,uAin Eq. 1 and the scatteris ing current 0.2 nA in Eq. 2, wherethe for currentis calculated a bias scattering voltageof V= 0.1 V and a lead bandwidthof 4 eV. This differenceof four betweenthe two curordersof magnitude that rentsis an indication the time interval betweentwo ET eventsin a A-L-B tunneljunctionis very large.It follows that thereis no phaserelationbetween ET the elementary events,nor a regular of distribution electrondeliveryto the tunneljunctionover time.This Schottky that electrondelivery noise indicates process to the junctionis a Poissonian in time (48). Each ET event can be coherent[under as considered quantum in conditionsdiscussed Decoherence and Relaxation (InelasticEffects)]. The overall is tunneling not coherent,but measured noisy.Thereis roomfor extensiveimof provement the sourceto take advanwith tage of the fast ET rate compared the very smallrate of electrondeliveryto the junction. of This discussion the sourceand detecelectronsmayhold for tion of tunneling junctionin the linearpartof anytunneling to Application a its I-V characteristic. tunneljunctioncan metal/molecule/metal and clarifyinterpretation nomenclature. of conductance the First,the measured junctionis not the metal-molecule-metal of "conductance the moleculeitself"nor ET the intrinsic rate throughthe molecularwire. It is simplythe rate of deliveryof electronsto the junction.Of course,this deliveryrate mustbe lowerthanET rate throughthe moleculeto avoidanycharge pile-upin the junction.Second,there is voltage, little electronflux at low-bias in which(as discussed the next section)

impliesthat for a virtualresonancetunnel processwherethe biasvoltageV is lower of than anyelectronicresonance the mo"electron lecularwire, the appellation wire"may througha molecular transport in not describethe real processoccurring junction.Third,one can the molecular as definethe contactconductance the partof the A-L-B junctionconductance of independent the lengthof the molecuis larwire (49). This conductance a measure of the abilityof the molecule/metal atomicscalejunctionto ease both the and conversion the classical-quantum at occurring the quantum measurement level.Both processes junctionmicroscopic in are summarized one constant,and workremainsto be done to disentangle of the characterization the two processes.
A Transport Phenomenon or a Guide for ExcchangeInteractions

in At low-biasV (as discussed the preceding section),very few electronsare rewire in the placedon the molecular elecregime.Each transferred tunneling tronis localizedmainlyto the electrodes wire:The moand not on the molecular lecularwire is not reducedor oxidized. The This processis purelyquantum: mostatesmerelyinlecularwire quantum state spaceof the A-bB creasequantum reptrajectory systemto open a quantum resenting ET eventbetweenA and B. the the Withoutthis state spaceexpansion, ET betweenA and B will be too slow. at Evenwith it, elasticscattering the electrode/moleculeinterfacewill reduce whichis the the valueof the conductance, view of the is "conductance scattering" Landauer formula(50). inWhenthe electronictransparency creasestowardunity,the electronicstates begin to delocalizealong of the electrodes the molecule,and a regimeof ballistic can transport be reached(in the absence where of vibroniccouplingor resonance), at least one excesselectroncan be (on alongthe molecular average)delocalized a wire.At low transparency, molecular wire can be betterseen as a partialguide interactions for the electronicexchange betweenthe two metallicelectrodesof the supA-L-B junctionthan as a material flux of electrons portinga permanent (51). The largedifferencebetweenthe ET rate is a good piece rate and the tunneling of evidencethat thereis no permanent wire junction, electronflux in a molecular electronic even if there is a permanent by interaction introduced the molecular wire in A-bB. Of course,an ET event exchange can be viewedas an information betweenA and B via L. The information the exchanged classical, presenceof an is state in electronprepared a nonstationary and locatedon A. Thereis no knownway of yet to controlin detailthe preparation
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a by this state,for example, preparing peculiarphasein the mixingof the molecuin lar orbitalinvolved the definitionof the A--L-B initialstate.We do not have state enoughcontrolyet of the quantum by of the electronsdelivered the elecwire to be able to trodesto the molecular between information quantum exchange A and B. an characterize exManyparameters of guide:the strength changeinteraction the the interaction, level of dissipation effects, of and importance the dispersion the the bandwidth, noise level, and the of capacity a channel communication wire in the tunformedby the molecular nel regime.Aside fromthe interaction density)and some vi(spectral strength of broniccomponents the dissipation, are none of the otherparameters accessibecausethe ble to simpleI-V experiments does not provideany intensity current aboutthem. directinformation
Decoherence and Relaxation (Inelastic Effects)

and decoherence relaxTwo phenomena, (discapability ation,limitthe quantum wire to cussedabove)of a molecular betweenmetallic information exchange increase with Both phenomena electrodes. and temperature lengthof the increasing wire (39), whichimpliesthat the ET time betweenelectrodesis becominglong relatime characteristic tive to some internal mediumdefiningthe of the molecular guide. exchange of Decoherence.Preparation the ET pro-

wire?In packetmovingalonga molecular effect,thisbehavsearchfor a supertunnel ior wouldprovidea wayto minimizeW3 and to couplethe A and B electrodes A over largedistances. firststep in this was direction to recognizethatthe specthe tralsecondmomentdescribing molecin level distribution ularwire electronic controlenergyis the secondparameter ling 13afterthe highestoccupiedmolecuoccupiedmolecular lar orbital-lowest wire (39, 55). orbitalgap of the molecular wire architecture Findinga molecular distribution to optimizethis second-order will lead to very small3. Unfortunately a of for this optimization V12, simpletunnelingjunctiondoes not accessall virtual This incompleteness electronicexcitations. beof is one explanation the difference tweenEqs. 1 and 2, as can be clearlyobI-V servedin electronic characteristics recordedon a singlemoleculewith a metal surmicroscope tunneling scanning tip face-molecule-metal apextunneljuncbe tion.The recordedspectracan usually througha quanas interpreted tunneling tum systemshowingonlyvery simple (56). How a excitations monoelectronic (selecting) junctionis filtering tunneling virtualexcitations the relevantelectronic to createa givenchannelis essentially from the an open question.Deviations expectedsimple(57) I-V curvesare somemicrotunneling timesseen in scanning scopeI-V spectraon singlemolecules(29) understood. and are not yet completely

with equallyspacedcharging staircase becauseof vibroniccoupeaks,essentially has pling.Thisobservation indeedbeen olion madein measurements conductive (59). gomerstructures and betweenvibrations The interaction for statesis responsible manyof electronic in phenomena molecthe most important peaks vibrational including ularmaterials, prononadiabatic in electronicspectra, Jahncessesof manytypes,including and Tellerdistortions, the characteristic with transassociated processes activation polymers(60-62). port in conducting These samevibroniccouplingeffectsare in important expectedto be extremely electronics. certainaspectsof molecular In this section,we verybrieflydiscuss suchvibroniccouplingin inelasticelectron (IETS),the mechspectroscopy tunneling fromcoherenttunneling anistictransition and processes, in some of to hopping-type in of behaviors transport the characteristic negative including junctions, molecular and mechanisms resistance differential behavior. hysteretic/switching
IETS spectraand line coupling: Vibronic firstdevelshapes.The IETSexperiment,

Inelastic Effects (Relaxation). Molecular (1-9) differsfrom moretradielectronics in electronics several tionalsemiconductor cess by the tunnelsourceon the left of one the A-L-Bjunctioncreatesa wavepacket, crucialways.An important first (58) whichis supposedto reachthe rightelec- pointedout by Yablanovich is that effiibitvibronic trodeand be detected.Wavepacketprop- moleculesnearlyalways spectrashowStokes Molecular so agationis dispersive, it is very difficult coupling: geshiftsand the excitedstate minimum of to optimizethe chemicalstructure a ever the wire to ensureperfect(quanometryof moleculesis hardly molecular just tumyield of unity)wavepacketpropaga- same as the groundstate geometry, as ions almost of tion. Some componentof the wavepacket the behavior molecular in will be phase-shifted time,leadingto a alwaysdiffersfromthat of the stablemolecules.The absenceof suchvibroniccouof deformation the wavepacket.As a plingin siliconis one of the important in consequence, the coherenttunneling decaywith aspectsof siliconsemiconductors, giving regimewith a gap, exponential = as geometries the eleclengthof the electroniccouplingV12(n) stable,unchanging changes.Becausethis tronicpopulation exp(-,BL)betweenthe electrodes VO(n) molecuabsenceis not true in molecules, wire will occur, throughthe molecular will lar electronics showseveralimportant where,Bis an inversedecaylengthof the from siliconelectronics. challenge differences process(39, 52). A fascinating semiconducin wire For example, traditional findinga peculiarmolecular involves staircase" trajec- tors the so-called"Coulomb or structure wavepacketquantum dispersionless regimeoccurswhen the couplingbetween tory controlto approach a (usually quantum of motion.The secondordercharacter the the bridgestructure, weak is for dot) and the electrodes relatively equationis responsible /3 Schrodinger on to beingboundfrombelow (53). But ancompared the electronicself-energy equation,the Maxwell the dot. Underthese conditions, dot the othersecond-order propagaremarkable lead to a "coulomb equation,produces can chargemultiply, will of this with material negative In tion behavior staircase." molecules, charging we, also changethe geometries; therefore, index(54). Mightsuchstrange refractive Coulomb wave do not expecta straightforward be behavior inducedinto a quantum
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in oped (63-67) at the FordLaboratories vibrathe l950s, consistsof observing tionalside bandsin the I-V characteristics medium.Becausethese of anytransport coupeaksarisefrom electron/vibration pling,they are expectedto dependcritiThe callyon the natureof this coupling. of the examines dependence experiment current the voltage,the on the transport and, (conductance), more firstderivative of the specifically, secondderivative the IETS In current. these second-derivative to one spectra, sees peaksthatcorrespond of excitation a vibrainelasticbehavior, tionalmode on the wire. textbookdiscussions Fromstandard indi(67), one mightexpectthe behavior the catedin Fig. 4. Whenever applied voltageV is largeenoughfor an inelastic passeventto occursuchthat the current wire can deposit ing througha molecular to energycorresponding a singlequantum one of vibration, shouldsee an increasein flows.Thisbethe rate at whichcurrent haviorwouldbe expectedto give changes changesin the valin slope of the current, and ues of the conductance, peaksin the IETSbehavior. It is usefulto considerthe molecular of generalization the so calledLandauerwhichthe contacttime, during Buttiker in electronis actually contact tunneling bridge(the time in with the molecular Fig. 2 betweenthe injectionand the release of this electronto the oppositeelec(68) approximation trode).A reasonable can be derivedon the basisof the original (69), extendedto deal argument Buttiker wire, type with a tight-binding molecular whichyieldsthe approximation
Joachim and Ratner

www.pnas.org/cgi/doi/10.1073/pnas.0500075102

dG/dV d2I/dVz /

Elastic tunneling eV < he

-

g(E) = gOTr{rt(E)G(E)rR(E)G+(E)}.
-hv
V o tv

50
X

l O0
.

Appiied Bias (mV) 150 200 250

, , j

300

350

[4] Hereg, gOX G, andL denote,respecr, tively,the conductance, atomicunit of the conductance (12.9kQ)-1, the mixingof the molecular wire with the electrodeon the left (L) and right(R) sides,and the Green'sfunction(72-75) for propagation of the electronthrough bridgestructhe ture.The couplings, are proportional r, to the escaperate of electronsfrom the molecule to the two electrodes. The Green's functionitself is takensimplyas

20-1.5 1 0 " |\ l,\t

A
/ \

1E

/
G

= dT/dV
r '
V

- hv
A

hV

X O

500
_

1000 1 500 2000 Wavenumbers 1) (cm

.

2500

hv I

Fig. 4. Schematic illustrationsof the IETS measurement. The cross-sections for the elastic and inelastic tunneling are (to a firstt rough approximation)additive,so that when the applied voltage exceeds a characteristic vibrationalenergy on the molecule, one expects to see changes of slope in the current,of value in the conductance,and peaks in the IETS (second derivativeof the current)structure (M. A. Reed, personal communication).

G-1 = (E-H

i8)=0+r

[5]

where H is the full-systemHamiltonian. Expanding conductance the the and currentaroundthe geometricminimum, one can writethe Green'sfunctionas Gij(E,{Q})-Gij(E,0) + +12 GiJQ(y E

Fig.5 Calculated(upper line) (AN Troisi,personal communication) and measured (lower line) (71) IETSspectra of an ortho-phenylene ethynylene molecule with a nitro substituent and gold electrodes. The peaks correspond to specific normal coordinates of the molecule.

a [6]

TC NA/AEG.

[3]

The contacttime, Tc, inversely is proportionalto AEG, the excitation between gap the injectionenergyand the isolated bridgefrontierorbitalenergy,and increaseswith the number, of repeat N, groupsin the wire. Thisform is actually a straightforward generalization the unof certainty principle, it has important but physical implications: largegaps (for For example(r-bonded systems)and short wires,Tc be of order10-l6 s, far too will shortfor significant vibroniccoupling.For smallergaps ( 7r-electrons) longer and wires,the contacttime can increaseto become of the orderof a vibrational period (39). One then expectsadequatetime for vibroniccouplingto operate.Thus,for long bridgesand r-type systems, vibronic couplingshouldbe moreimportant than for v-type systemsand shortbridges, in accordance with a numberof experimental observations 71). (70, For relatively voltagesand low temlow peratures (conditions < hx andeV s kT hst), where Z is the molecular vibration frequency V is the appliedvoltage), and one can developa perturbative description of the IETSspectrum (93). Here it is assumedthat the vibroniccouplingis weak enoughthat no polarons(charged distortions on the molecular bridge)occur.The current elastic,and the inelasticpart is can be evaluated low-order by perturbation theorysimilarto the Herzberg-Teller analysis vibrational for structure elecin tronicspectra. Under these conditionsand fromEq. 2, the conductance be written(A. Troisi can and M.A.R.,unpublished data) in the standard Landauer-type model as
Joachim and Ratner

G1J-- AI28Gij/8QAIQ=O [7] The geometricderivativeof Eq. 7 determines the importanceof any particular vibrationalnormal coordinate,Q(,t, in the IETS spectrum.In this sense, it is a dimensionalcouplingconstantfor the intensities. One generally expectsthat a peak wouldappearin the IETSspectrum when the resonance condition, eV= hcl)ot, occurs.The areaof this peak, W,,e, is
W,x x goTr {r (EF)G (EF)rR

left and right),and the computational analysis restricted is now in consideration of a molecule,consistent with the molecularbridgeterminated the A and p by orbitals. Often, one expressesthe IETS spectrum in the form of the derivative quotient:
d2I/dV2

dI/d V whichis plottedagainst voltageV. One then expectsthat therewill be a peak at the resonance condition, eV= hcoX,. The peak intensity be givenby the ratio will R,,,(EF) |GAp(Ef) =
12/ |

GAp(EF)

12-

[9]

Physically, perturbative this treatment treatsthe inelasticcomponentas a perturassuming (EF)G+(EF)}[8] bationof the elastictransport, that the systemis very close to equilibAlthoughthis is an attractive formal riumbecausethe vibrational frequencies scheme,its computational implications are are all less 0.2 eV. In addition, gatethe difficult: One must dealwith calculating wayorbitalapproach thatthe vibrasays the current itself,the structure, specthe tionalstructure the bridgeis, to a on traldensitiesr, and the full dependence reasonable extent,separable fromthe of the Green'sfunctions(including selfspectral densitiescouplingthe bridgeto energies)on the vibronicnormalmode. Troisi(A. Triosi,personalcommunica- the electrodes. Fig. 5 showsa comparison betweenthe tion) considered simplification the a of experimental IETSspectrum (71) of the problemthat leadsto a tractable compuoligophenyleneethynylene moleculeand tationand stillprovides both good fits to the computation, carriedout by using the experiment substantial and experistandard densityfunctional theory.The mentalinsight(A. Troisiand M.A.R.,unthreemajorbandsof the IETSspectrum published data).He arguesthat one can are verywell produced the simulation: by glean a greatdeal of information about The high-frequency signalnear 2,211 the molecular vibronicdirectionand its cm-1 is due to the triplebond symmetric importance IETSby ignoring, spirit in in the of weak couplingand perturbation theory, stretch; peak at 1,582cm-1 is due to and effectsarising from the spectraldensities, the doublebond stretch; the C/C/C bend,largelylocalizedon the aromatic r. He then definesa "gateway" orbital, to whichacts as a bridgebetweenthe molec- rings,givesthe majorcontribution the peak at 1,100cm-1. Comparable ularentityand the electrodeitself.These results gateway orbitalsare labeledA and p (for are foundfor othermolecules.
PNAS | June 21, 2005 | vol. 102 | no. 25 | 8805

'*

Becauseno symmetry principles were involvedin this calculation, propensity behaviors(numerical selectionrules)are seen in the spectrum. The totallysymmetric representation peaksdominate. Moreover,the couplingconstantscharacterized in Eq. 7 indexthe IETSbehavior very well. The appearance peaksin the of IETSspectrum, the normalcoordinates at corresponding the fullysymmetric to vibrationsof the molecule,is strongevidence that the transport actually occurs throughthe molecule. Althoughthe simpleperturbative model developedin Eqs. 4-9 providesa good generaldescription, thereare manymore specificand challenging issues,for which the simpleperturbative analysis maynot be adequate. The firstof these involves the actualline shapesfor the vibronicfeaturesin the spectrum. This is a complicatedproblem, requiring self-consistent solutionsof the self-energies the vibrafor tionaland the electronicGreen'sfunctions (72-75). Althoughthese line shapesprovide important mechanistic insights, this analysis outsideour scope here. Signifiis cant effectsoccurwhen the vibroniccouplingbecomestrulystrong,and the next two sectionsdiscussthe mechanistic transitionfrom coherenttunneling hopping to behavior, the implications such and of strongcouplingin determining important, unusualspectral features7 such as negative differential resistance (NDR) and hysteretic/switching transport behaviors.
Mechanistic transition: Tunneling to hoppingg

mean that substantial energyis dissipated as heat.

Polarons, NDR, hysteric/switching and behavior in molecular junctions. Vibroniceffects
D -o
|}t$$4t$|1 XttlGtf * 1} j llf

\\
41|#14t1}11414}X1ti1{X4*1FtXtll(tl81**|||l

Netrate
s }1t1 g f 1111Wf 11*XU111114tWl{Ilt$IIiB$B$lti | ltl*titlElkl*t*gX |

ki

\
.\(MoheAreX]t tunn,.l,ng

distance
Fig.6. Schematicexpected behaviorfor intramolecularETreactionsand for conductance as a function of the length of the molecular bridge. The total rate is the sum of injectionhopping (incoherent motion), which i5 weakly distance-dependent, and coherent tunneling, which depends exponentially on distance.

For shortmolecule-transport structures, particularly thosewithoutconjugation, the Landauer-Buttiker argument Eq. 3 of suggests veryweakvibroniccouplingand elastictransport. This sense of the Landauerformulafollowsfrom a generalnonequilibrium Green'sfunctionapproach if only electronictermsare considered in the Hamiltonian. longerbridgesand For smallergaps,the vibroniccouplingshould becomemore important. In scanningtunneling microscope measurements, pioneering workby Ho's group (76-78) has indeedshowil,for a molecule on a semiconductor surfaceS an entire that vibrational progression be seen in can the IETSspectrum. Thisbehaviorcould be analyzed usinga variantof the selfby consistent Bornapproximation, when even the couplingcan become strong,allowing morethanone vibrational quantum be to involved the inelasticcurrent(79). in Perhapsthe most striking predicted behavioris a changein the mechanism from tunneling low temperatures short at and bridges a hopping-type to (incoherent) motionfor long wiresand smallinjection barriers 70). In molecular (39, junctions, as in intramolecular reactions, ET one actually expectsa mixture two mechaof nisms: the firstmechanism, In electrons
8806 | www.pnas.org/cgi/doi/10.1073/pnas.0500075102

simply tunnel across the barrier through the intervening states; as temperature increases, however, activated-type processes in which the electron is thermally excited to a higher level, thus reducing the possible tunneling distance, can become relevant (70, 80). For high fields, long wires and small injection gaps a fully activated process can occur. As discussed in Decoherence, the quantum ET events occurring at low temperatures lead to an exponentially decreasing current as a function of the interelectrode distance in the tunneling junction (Fig. 2). Upon activation, one expects diffuse hopping along the bridge, so that the length dependence on transport would be very shallow (generally 1/(A + BR), where A and B are constants depending on the particular experiment, and R is the distance between the electrodes) (Fig. 6). The transition from one of these mechanisms to another has been well characterized in situations like intermolecular ET processes in qr-electron species and DNA (39, 81, 82). For electron transport in actual wire junctions, we know of no direct observation of the transition indicated in Fig. 6; limiting regimes have clearly been seen, from the pure tunneling behavior (49, 83-86) in small oligoalkanes and phenylene-vinylenes (all of which are tunneling) to actual conductive polymers, which transport charge (at least at high temperatures) essentially by activated mechanisms (59). Although these transitions are perhaps the most striking indication of vibronic coupling and its effects in changing ET mechanism in molecular wires and they have been extensively discussed theoretically, direct experimental confirmation is still incomplete. In actual applications, the coherent and incoherent regimes could be quite important: Simply because the transport is incoherent does not necessarily

in molecular transport junctions have been stressed very recently, both theoreticallyand experimentally. indicated As above,localization the electronscan of lead to incoherent tunneling processes. Datta and collaborators havevery (87) recentlyextendedearlierworkconcerning the effectsof imageforceson molecular wire transport. Supposethat the two interfaces inare equivalent; example,supposethatthe for moleculewere more strongly coupledto the left A thanto the rightB electrodein Fig. 2. Then,localizedchargeon the molecule can get closerto the left electrode, building greaterimage-type a stabilization there andyieldingan asymmetry the in overallself-consistent electrostatic potential.Formally, can rewritethe Green's one functionfor transport throughthe molecularwire as
G-1(E)=(E-F-EL-R)
[10]

Here, the last two terms are the electronic self-energiesarisingfrom interaction between the molecule and the left and right electrodes,whereasF is the Fock operator,representing selfthe consistentone-electronHamiltonian that appearsfor any given appliedfield m any glven geometry. One can construct self-consistent a solutionto this problem, basedon a complete neglectof differential overlap-type semiempirical argument (88). A self-consistentelectrostatic potentialcan be found that dependson the changein electronic densityon the bridge.This expression enters the Fock operatorand can be in turn represented as
. .

V(i\p)

VLaplace

VPoisson

Vimage(^P)

[11]

The Poissonpartof the equationis approximated usingthe completeneglect by of differential overlappotential, which containsthe charging the screening and effects (p is the chargedensity).Laplace and imagepotentialsare calculated by usinga finite elementmethod,with boundary conditions by the local set chemical potentials the presenceof the in appliedelectrostatic potentialso thatany asymmetry the potentialprofilecan be in includedin an explicitfashionin termsof the self-consistent overallpotential. Application polarontheoryfor deof vice possibilities molecular in transport junctions, particular NDR and in for switching behavior, been developed has
Joachim and Ratner

O.8 1X0

w_ 3

n0- 2X[E

2(n

)]2+

(r/2)2

/2
0.E 0s4 O.2
olo ows
1.0 1.5

4
/} 2

(x 1

-:

t le

f 1+
/ ,i' * _ o _ * _

-10

10

m5

o
s

10
-E

tance spectrum of a conjugated molecularstructure. Note that Right examines only the positive voltage sweep regime.

Fig. 7. Computed (Lower) (89) and measured (Upper) (90) hysteretic behavior in the conduc-

byGalperin coworkers and (89). Their simplemodelconsistsof a wire representedby a singlesiteS containing single a electronic state and a singleharmonic oscillator Thiswire is placedbetweentwo electrodes, the vibration the moleand on culeis allowedto interact with phononsin theenvironment (whichcouldbe electrodes a solvent).The Hamiltonian or can thenbe expressed as H socoCO
+ 8ka

(highlyreminiscent the mean-field of treatment magnetic of systems general). in Hysteresis loops mightbe attainableS as shownin Fig. 7 Whenso lies in the windowbetweenZL and ZR, one wouldnormally expectresonanttunneling occur.If, however, to polaronformation lowersthe energysufficientlyby reorganization effectsthat dropsbelowthe chemical potentialof the low-voltage electrode,then the current shouldabruptly off, as is seen in the turn NDR experiments. 8 showssucha Fig. Hel=fo+CoCo prediction arising fromthe meanfield model,compared with the experimentally + E [ kC k C k + VkC o C k + h .c .], observedstructure. Both the temperature k dependence the voltagedependence and 1 [l 3 ] of the calculated NDR spectrum agree with thatreported the experimental in Here, the renormalized site energy e0 deliterature. pends on the occupation of the site, noIn this overview, havefocusedon we Rerenorma lze( energy 1S threetopics(largely unexplored) moof lecularelectronics go beyondsimple that 80(no) = so 2erergn' 114] transport junctions, the questionof like where the reorganization improving efficiency a tunneljuncthe of energyis given by tion as a sourcevf electronprepared a in quantum state superposition, notion the reorg-M coo/[e + (7/2) ], of the superexchange transport junctionas a guidefor those electrons pointingto[15] wardquantum information, the role and of vibroniccouplingand inelasticity the with Sy in beingthe phononlifetime. intramolecular eventsdetermining In the wide-band the limitand at steady physical characteristics this guiding. of state,one can rewrite occupation the on The firstand the last of these topicswill the level in termsof a contourintegral certainly comprise majorfoci of the field overthe lesserGreen'sfunctionin the in the nearfuture. form
. , . .

c0, a, ck and b are the destruction operators for the bridge electronic state, bridge vibrational state, bulk electronic state, and environmental phonon, respectively.'I8his Hamiltonian is characteristicof linear coupling to form a polaron plus an injection model at the interface. In the spirit of the Born-Oppenheimer approximation,it is possible to separate the electronic and vibrational parts of the Hamiltonian. 'Rheelectronic term then reads

de

rtft(E)

re(R(E)
1.2
1.0

C16] HerefL andfRare the Fermifunctions on the left and rightelectrodes, respectively, with the spectral density
_s

0.8
t

k ak

0.6 0.4 0.2

o.0
l * l w w & l 8 8 8

(91)

L,R + E ( VkC 0 Ck + k

h .c . ) a)

r = rR+ rL

[17]

IVilt- 1 pA
l n

+ McOcO(a+ +

+ , [ co3b b{3+ Uf3(b + b{3) {3, {3

* (a+ + a)] + a+acoO. [12]

Herethe terms e0, 00, k,Cl)are the electronic energylevel on the wire, the vibrational frequency the wire,the on electronic energiesin the electrodes, state and vibrational the frequency the phoof nons, respectively. couplingconstants The Vk, andM are respectively injecUs, the tion tunneling matrix elementbetween the molecular wire and the bridge,the phonon/vibration interaction, the viand bronic couplingon the molecule.Finally,
Joachim Ratner and

Eq. 17 is the self-consistency condition: The population, on the bridgedeterno, minesthe polaronshiftedenergye0, whichin turnredetermines Thiscondino. tion becomesquitestraightforward the in limitof T = Oat equilibrium, - ZLZR Thenthe integral be performed, can and the resultis
-

0.0

0.5

1.0 1.S Voltage (V)

s

2.0

2.5

lXlo@)

if
2S

S 15

(89)

nO --arctan(x) 7r

rx 80-y 48reorg 2 reorg Solving these equations self-consistently yields eitherone or threeroots.When three rootsare seen, a typicalhysteresis situation occurs,arising frommultistability

Q.U

U.S

1.U

l S

Z.9

2.5

[18]
Fig. 8.

Y (v)

Measured (Upper) (91) and calculated (Lower) (89) negative differential resistance feature the conductance measurement of the in sketched molecule. The model explainsthe result based charging of the molecularjunction. on
June 21, 2005
|

PNAS |

vol. 102

no. 25

8807

Note Added in Proof.While this manuscript was in production,an articlewas published that offers a specificview of some aspects computing of actualmolecular-based schemes(92). C.J. thanksthe NanoScience Group at the Centre National de la Recherche Scientifique (Toulouse, France) and his partnersin
1. Petty, M. C., Bryce, M. R. & Bloor, D. (1995) Introduchon to Molecular Electronics (Oxford Univ. Press, Oxford). 2. Aviram, A., ed. (1992) Molecular Electronics: Science and Technology (Am. Inst. Phys., College Park, MD) 3. Aviram, A. & Ratner, M. A., eds. (1998)Ann. N.Y. Acad. Sci. 852,1-370. 4. Jortner, J. & Ratner, M. A., eds. (1997) Molecular Electronics (Blackwell Scientific, Oxford). 5. Reed, M. A. & Lee, T., eds. (2003) Molecular Nanoelectronics (Am. Sci., Stevenson Ranch, CA). 6. Reimers, J., Picconatto, C., Ellenbogen, J. & Shashidhar, R., eds. (2003) Ann. N. Y. Acad. Sci. 1006, 1-330. 7. Cuniberti, G., Fagas, G. & Richter, K, eds. (2005) MolecularElectronics(Springer,Berlin). Introducing 8. Seideman, T. & Guo, H. (2003) J. Theor. Comp. Chem. 2, 439-458. 9. Salomon, A., Cahen, D., Lindsay, S., Tomfohr, J., Engelkes, V. B. & Frisbie, C. D. (2003)Adv. Mater. 1S, 1881-1890. 10. Cuberes, M. T., Schlittler, R. R. & Gimzewski, J. K. (1996) Appl. Phys. Lett. 69, 3016-3018. 11. Chuang, I. L., Vandersypen, L. M. K., Zhou, X. L., Leung, D. W. & Lloyd, S. (1998) Nature 393, 143-146. 12. Joachim, C. & Gimzewski, J. K. (1997) Chem. Phys. Lett. 265, 353-357. 13. Aviram, A. & Ratner, M. (1974) Chem. Phys. Lett. 29, 277-283. 14. Carter, F. (1983)J. Vac. Sci. Technol. B 1, 959-968. 15. Joachim, C., Gimzewski, J. K. & Aviram, A. (2000) Nature 408, 541-548. 16. Yi, J. & Cuniberti, G. (2003)Ann. N.E Acad. Sci. 1006, 306-311. 17. Joachim, C. (2002) Nanotechnology 13, R1-R7. 18. Datta, S. (2005) Quantum Transport: Atom to Transistor(Cambridge Univ. Press, New York). 19. Nitzan, A. & Ratner, M. (2003) Science 300, 1384-1389. 20. Troisi, A. & Ratner, M. A. (2003) in Molecular Nanoelectronics, eds. Reed, M. A. & Lee, T. (Am. Sci., Stevenson Ranch, CA). 21. Heath, J. R. & Ratner, M. A. (2003) Phys. Today 56 (3), 43-49. 22. Ebling, M., Ochs, R., Koentopp, M., Fischer, M., von Hanisch, C., Weigend, F., Evers, F., Weber, H. B. & Mayor, M. (2005) Proc. Natl. Acad, Sci. USA 102, 8815-8820. 23. Ellenbogen, J. C. & Love, C. (2000) Proc. IEEE 88, 386-426. 24. Walter, D., Neuhauser, D. & Baer, R. (2006) Chem. Phys. 299,139-145. 25. Fiurasek, J., Cerf, N. J., Duchemin, I. & Joachim, C. (2004) Physica E 24, 161-172. 26. Moresco, F. & Gourdon, A. (2005) Proc. Natl. Acad. Sci. USA 102, 8809-8814. 27. Guisinger, N. P., Yoder, N. L. & Hersam, M. C. (2005) Proc. Natl. Acad. Sci. USA 102, 8838-8843. 28. Nazin, G. V., Wo, S. W. & Ho, W. (2005) Proc. Natl. Acad. Sci. USA 102, 8832-8837. 29. Repp, J., Meyer, G., Stojkovic, S., Gourdon, A. & Joachim, C. (2005) Phys. Rev. Lett. 94, 0268002683. 30. Guisinger, V. P., Greene, M. E., Basu, R., Baluch, A. S. & Hersam, M. C. (2004) Nano Lett. 4, 55-59.

the EuropeanBottom-Up Nanomachines project, the Consortiumfor Hamiltonian Computing,the Atomic and Intramolecular MolecularManipulationas a new Tool for Science and Technologynetwork,and the for Pico-Insideconsortium manyilluminating M.A.R. thankshis manycollabodiscussions. A. rators,particularly Nitzan,V. Mujica,A. Troisi,M. Galperin,Z. Bihary,and Y. Xue, and the Departmentof Defense Multidisci31. Langlais, V., Schlittler, R. R., Tang, H., Gourdon, A., Joachim, C. & Gimzewski, J. K. (1999) Phys. Rev. Lett. 83, 2809-2812. 32. Bonifazi, D., Spillmann, H., Kiebele, A., de Wild, M., Seiler, P., Cheng, F. Y., Guntherodt, H. J., Jung, T. & Diederich, F. (2004) Angew. Chem. Int. Ed. 43, 4759-4763. 33. Datta, S., Tian, W., Hong, S., Reifenberger, R., Henderson, J. I. & Kubiak, C. P. (1997) Phys. Rev. Lett. 79, 2530-2533. 34. Moresco, F., Gross, L., Alemani, M., Rieder, K. H., Tang, H., Gourdon, A. & Joachim, C. (2003) Phys. Rev. Lett. 91, 036601. 35. Liu, S., Maoz, R. & Sagiv, J. (2004) Nano Lett. 4, 845-851. 36. Rosei, F., Schunack, M., Jiang, P., Gourdon, A., Joachim, C. & Besenbacher, F. (2002) Science 296, 328-331. 37. McConnell, H. M. (1961)J. Chem.Phys.35, 508-515. 38. Halpern, J. & Orgel, L. E. (1960) Discuss. Faraday Soc. 29, 32-41. 39. Nitzan, A. (2001)Ann. Rev.Phys.Chem. 52, 681-750. 40. Joachim, C. (1987) J. Phys. A 20, L1149-L1155. 41. Launay, M. P. (2001) Chem. Soc. Rev. 30, 386-397. 42. Galperin, M., Segal, D. & Nitzan, A. (2000) J. Chem. Phys. 111,1569-1579. 43. Nakamura, Y., Chen, C. D. & Tsai, J. S. (1997) Phys. Rev. Lett., 79, 2328-2331. 44. Devoret, M. H., Esteve, D. & Urbina, C. (1992) Nature 360, 547-553. 45. Buttiker, M., Imry, Y., Landauer, R. & Pinhas, S. (1985) Phys. Rev. B 31, 6207-6215. 46. Joyez, P., Esteve, D. & Devoret, M. H. (1998) Phys. Rev. Lett. 80,1956-1959. 47. Doyen, G. (1993) J. Phys. C 5, 3305-3312. 48. Lee, H. & Levitov, L. S. (1996) Phys. Rev. B 53, 7383-7391. 49. Wold, D. J. & Frisbie, C. D. (2001) J. Am. Chem. Soc. 123, 5549-5556. 50. Beenakker, C. W. J. & van Houten, H. (1991) in Solid State Physics: SemiconductorHeterostructures and Nanostructures, eds. Ehrenreich, H. & Turnbull, D. (Academic, New York), pp. 1-228. 51. Kaun, C.-C., Guo, H., Grutter, P. & Lennox, R. B. (2004) Phys. Rev. B 70, 195309. 52. Joachim, C. (1987) J. Chem. Phys. 116, 339-349. 53. Magoga, M. & Joachim, C. (1998) Phys. Rev. B 57, 1820-1823. 54. Pendry, J. B. (2000) Phys. Rev. Lett. 85, 3966-3969. 55. Lahamidi, A. & Joachim, C. (2003) Chem. Phys. Len. 381, 335-339. 56. Joachim, C. & Gimzewski, J. K. (1995) Euro. Phys. Lett. 30, 409-414. 57. Xue, Y. & Ratner, M. A. (2005) Int. J. Quantum Chem. 102, 911-924. 58. Yablonovitch, E. (1989) Science 246, 347-351. 59. Kubatkin, S., Danilov, A., Hjort, M., Cornil, J., Bredas, J.-L., Stuhr-Hansen, N., Hedegard, P. & Bjornholm, T. (2003) Nature 425, 698-701. 60. Kuznetsov, A. M. (1995) Charge Transferin Physics, Chemistry and Biology (Gordon & Breach, New York). 61. Kuznetsov, A. M. & Ulstrup, J. (1998) Electron Transferin Chemistryand Biology:An Introduction to the Theory (Wiley, New York). 62. Barbara P. F., Meyer, T. J. & Ratner, M. A. (1996) J. Phys. Chem. 100,13148-13168.

plinaryUniversityResearchInitiatives/Defense UniversityResearchInitiativeon Nanothe technologyProgram, Defense Advanced of ResearchProjectsAgencyApplications the MolecularElectronicsProgram, National for Science Foundation/Network Computaprogram,the Chemistional Nanotechnology try Divisionsof the NationalScienceFoundation, and the Office of Naval Researchfor support.
63. Jaklevic, R. C. & Lambe, J. (1966) Phys. Rev. Lett. 17, 1139-1 140. 64. Adkins, L. J. & Phillips, W. A. (1985) J. Phys. C Solid State Phys. 18, 1313-1346. 65. Wolf, E. L. (1985) Principles of Electron Tunneling Spectroscopy (Oxford Univ. Press, New York). 66. Hipps, K. W. & Mazur, U. J. (1993) J. Phys. Chem. 97, 7803-7814. 67. Hansma, P., ed. (1982) Tunneling Spectroscopy (Plenum, New York). J., J., 68. Nitzan,A., Jortner, WiLkie, Burin,A. L. & Ratner, M. A (2000)J. Ps. Chem.B 104, 5661-5665. 69. Buttiker,M. & Landauer,R. (1985) Phys.Scr.32, 429. 70. Datta, S. (2004) Nanotechnology 15, S433-S451. 71. Kushmerick, J. G., Lazorcik, J., Patterson, C. H., Shashidhar, R., Seferos, D. S. & Bazan, G. C. (2004) Nano Lett. 4, 639-642. 72. Galperin, M., Ratner, M. A. & Nitzan, A. (2004) J. Chem. Phys. 121, 11965-11979. 73. Mii, T., Tikhodeev, S. G. & Ueba, H. (2003) Phys. Rev. B 68, 205406. 74. Lundin, U. & McKenzie, R. H. (2002) Phys. Rev. B 66, 075303. 75. Meir, Y. & Wingreen, N. S. (1992) Phys. Rev. Lett. 68, 2512-2515. 76. Stipe, B. C., Rezaei, M. A. & Ho, W. (1998) Science 280, 1732-1735. 77. Lee, H. J. & Ho, W. (1999) Science 286, 1719-1722. 78. Gaudioso, J., Lauhon, L. J. & Ho, W. (2000) Phys. Rev. Lett. 85,1918-1921. 79. Galperin, M., Ratner, M. A. & Nitzan, A. (2004) Nano Lett. 4, 1605-1611. 80. Burin, A. L. & Ratner, M. A. (2003) J. Polym. Sci. Part B: Polym. Phys. 41, 2601-2621. 81. Jortner, J. & Bixon, M. (1999) in Advances in Chemical Physics, eds. Prigogine, I. & Rice, S. (Wiley, New York), p. 106. 82. Rice, S. A., Berry, R. S. & Nitzan, A., eds. (2004) Israel J. Chem. 44, 1-408. 83. Reichert, J., Weber, H. B., Mayor, M. & Lohneysen, H. V. (2003) Appl. Phys. Lett. 82, 4137. 84. Wang, W., Lee, T., Kretzschmar, I. & Reed, M. A. (2004) Nano Lett. 4, 643-646. 85. Smit, R. H. M., Noat, Y., Untiedt, C., Lang, N. D., Hemert, M. C. V. & van Ruitenbeek, J. M. (2002) Nature 419, 906-909. 86. Reichert, J., Ochs, R., Beckmann, D., Weber, H. B., Mayor, M. & Lohneysen, H. V. (2002) Phys. Rev. Lett. 88,176804. 87. Zahid, F., Ghosh, A. W., Paulsson, M., Polizzi, E. & Datta, S. (2004) arXiv: cond-mat/0403401. 88. Ratner, M. A. & Schatz, G. C. (2002) Introduction to Quantum Mechanics in Chemistry (PrenticeHall, Englewood Cliffs, NJ). 89. Galperin, M., Ratner, M. A. & Nitzan, A. (2005) Nano Lett. 5, 125-130. 90. Blum, A. S., Kushmerick, J. G., Long, D. P., Patterson, C. H., Yang, J. C., Henderson, J. C., Yao, Y., Tour, J. M., Shashidhar, R. & Ratna, B. R. (2005) Nat. Mater. 4, 167-172. 91. Chen, J., Reed, M. A., Rawlett, A. M. & Tour, J. M. (1999) Science 286, 1550-1552. 92. Remacle, F., Heath, J. R. & Levine, R. D. (2005) Proc. Natl. Acad. Sci. USA 102, 5653-5658. 93. Troisi, A., Nitzan, A. & Ratner, M. A. (2003) J. Chem. Phys. 118, 5782-5788.

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Joachim and Ratner