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journal of modern optics 2003, vol. 50, no. 15–17, 2393–2410

modern optics 2003, vol. 50, no. 15–17, 2393–2410 Current-driven dynamics in quantum electronics TAMAR

Current-driven dynamics in quantum electronics

TAMAR SEIDEMAN

Department of Chemistry, Northwestern University 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA; e-mail: seideman@chem.northwestern.edu

( Received 12 March 2003; revision received 22 April 2003 )

Abstract. We suggest that inelastic electron tunnelling via molecular-scale electronics can induce a variety of fascinating dynamic processes in the molecular moiety. These include vibration, rotation, intermode energy flow and reaction. Potential applications of current-induced dynamics in molecular- scale devices range from new forms of molecular machines and approaches to enhancing the conductivity of molecular wires, to new directions in nanochem- istry and nanolithography. Understanding the molecular properties that encourage current-triggered dynamics is relevant also to the design of devices that would be guaranteed to remain stable under current. We discuss the qualitative physics underlying current-driven dynamics, briefly sketch a theory developed to explore these dynamics, describe a few examples from recent and ongoing numerical work and note avenues for future research.

1. Introduction

Considerable theoretical effort has been devoted in recent years to the problem

of molecular-scale electronics. This research [1–17] has been fuelled by the

fascinating physics of conductance at the molecular level, by the anticipation for technological applications and by the development of experimental techniques to produce and characterize molecular-scale electronics [18–36]. Reviews of the theoretical and experimental aspects are given in [17] and [21] respectively.

A recent special issue on transport in molecular wires [37] provides a useful

up-to-date overview of this exciting field. The combination of theoretical and numerical work in this area has yielded substantial insight into the response of the

conductivity to several general attributes [2–8], as well as quantitative predictions

of the conductance of a variety of specific systems [10–15].

A problem of significant fundamental interest, which may also carry practical benefit and which is only starting to be explored, is the effect of the current on the molecule. Recent theoretical work [38], supported by indirect experimental evidence, suggests that inelastic tunnelling via molecular-scale devices can induce a variety of dynamic processes in molecular heterojunctions. These include

vibration, rotation, intermode energy flow and reaction. The mechanism through which a tunnelling current at the mild conditions typical of molecular electronics research can trigger large-amplitude motion of a massive molecular backbone is simple and general. For applications such as molecular wires, favourable candidates are molecules that offer resonances in energetically accessible regimes. Resonance-mediated conductance is efficient

Journal of Modern Optics ISSN 0950–0340 print/ISSN 1362–3044 online # 2003 Taylor & Francis Ltd http://www.tandf.co.uk/journals DOI: 10.1080/0950034034032000120876

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and at most weakly distance dependent. By contrast, direct tunnelling falls exponentially with increasing distance. Resonance conductance is often inelastic. Provided that the initial and resonant electronic states are displaced in equi- librium, the system evolves during the resonance lifetime. Upon electronic relaxation the molecule carries internal excitation which may suffice to trigger chemical dynamics before relaxing to the initial vibrational state [38]. Current-triggered dynamics in nanosystems carries potential implications and applications in several fields.

(i) New forms of molecular machines. The area of artificial molecular machines [39] has been evolving rapidly for nearly two decades, leading to laboratory-made turnstiles, shuttles; switches and rotors, driven by light, chemistry or electrochemistry. On the one hand, this work points to a host of potential technological applications [39]. On the other hand, it reveals the need for new forms of molecular machines, which could be addressed individually, thus eliminating the ensemble average that is inherent to the solution phase. Current-triggered dynamics in molecular heterojunctions could make a route to that end. We envisage using resonant inelastic current to deposit energy selectively into a given mode and hence to induce directed motion of the molecular component. (ii) Dynamic modification of the conductivity of molecular wires. Often in

molecular wires the conductivity depends sensitively on the structure of the molecule [22]. An example is the biphenyl family, where the conductivity changes by over an order of magnitude as the torsion angle between the rings varies between zero and p /2. In these systems, torsion may be expected to ensue resonance tunnelling since the ionic states of biphenyl differ substantially from the ground neutral state in equilibrium configuration, specifically along the torsion angle. Current-triggered large-amplitude vibration may likewise modify the conductivity of wires. An experimental study of electron transfer from a metal surface to a molecule [40] found the electron transfer probability to be greatly enhanced by excitation of the molecule to high vibrational levels. Clearly, one can envisage systems where molecular motion inhibits the conduc- tivity, because the equilibrium is ideally configured for electron transfer to take place.

(iii) Nanochemistry. An intriguing possibility is that of using a scanning tunnelling microscope tip to induce surface reactions that do not occur spontaneously and to study them on a single-molecule, site-specific level. One class of systems of interest is the reactions of the common gas sources used for thin-film growth on, and doping of, Si by chemical vapour deposition (NH 3 for N, PH 3 for P, and AsH 3 for As, for instance). The thermal reactions currently used by advanced growth and doping tech- nologies are not ideal to that end, as is evident from the broad disparity between observations of different laboratories [41] and from the variety of

undesired effects reported [42]. The current-triggered approach may introduce an opportunity of controlling the outcome.

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The design of current-immune devices relies on understanding the molecular properties that encourage current-triggered dynamics. (v) Opportunities in molecule-scale lithography. Nanolithography based on current-induced desorption of H atoms from Si(100) is an established field with a variety of applications [43–47]. Organic molecules may offer advantages. In the adsorbed state conjugated organics support low-energy resonances (lying close to the Fermi level), corresponding to much lower voltages than those used for H desorption from silicon; hence smaller tip– surface separations and improved resolution. Further, as discussed in [48], the properties of organic adsorbates can be tuned via functional group substitution, providing a means of control over the process.

In the next section, we outline a recently developed theory of current-driven dynamics in molecular devices. Section 3 describes several applications and the final section concludes with an outlook to future research.

2. Theory and interpretation

We consider nuclear dynamics that are triggered by an inelastic resonance- mediated tunnelling event. In the tip–adsorbate–substrate environment, this would be a surface reaction induced by electron transfer from the tip to the surface or vice versa via an adsorbate-derived resonance. In the molecular wire environment, we envisage directed motion of the molecular moiety, induced by tunnelling from one electrode to the other via a resonance of the molecule þ electrodes Hamiltonian, as modified by the bias voltage. Formally the two prob-

lems are equivalent and can be studied within the same theoretical framework. Numerically, however, they differ substantially, as outlined below. The complete Hamiltonian is written as

ð1Þ

where H e describes the electronic dynamics and allows for hopping of electrons between the two electrodes via the adsorbate orbital, H N is a system-specific nuclear Hamiltonian and H eN is the non-adiabatic interaction coupling the electronic and vibrational motions. It is convenient to expand the Hamiltonian in eigenstates of H e , such that coupling between the extended electronic states of the two electrodes and the discrete state localized on the adsorbate is taken into account non-perturbatively. In this representation,

H ¼ H e þ H N þ H e N ,

H e ¼ X

c

y

c þ X c

y

c ,

ð2Þ

where j i and j i are stationary electronic states on the two electrodes and and , are the corresponding energies. The coupling is written in the H e representa- tion as,

H e N ¼ h N ðQÞ X ðh jr i h rj i c

;

y

c h n r ,

ð3Þ

Equation (3) adapts the coupling term used in several early studies of vibrational excitation of a linearly coupled harmonic oscillator to the problem considered here [49].

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where h N (Q) is a function of the nuclear coordinates Q, jri denotes the resonant

orbital and hn r i is

Assuming that the non-adiabatic interaction can be described within first-order perturbation theory, we express the reaction rate w as

its equilibrium occupancy.

w ¼ 2 2p

~

X

,

X

v

f i ð Þ½1 f f ð Þ jh v , jH e N j v 0 , ij 2 ð Þ,

ð4Þ

where jv 0 , i¼jv 0 ij i, jv , i¼jv ij i, jv 0 i is the initial vibrational state, a bound eigenstate of the nuclear Hamiltonian, and jv i is a final, bound or free eigenstate of the same Hamiltonian. We denote by the energy transferred from electronic into vibrational modes, ¼ , and the subscript to v serves as a reminder that the energy of the final state is restricted through energy conservation to above the initial state energy. In equation (4), v 0 denotes collectively the set of quantum indices specifying the parent state. In the case of a bound–bound process in the nuclear mode (such as intermode energy flow, rotational or vibrational excitation or a surface exchange reaction), v has a similar significance. In the case of a bound–free reaction in the nuclear mode (such as a desorption or a dissociation), v denotes the scattering energy and the quantum indices specifying the internal state of the free product. In the latter case, the v summation in equation (4) implies summation over the discrete indices and integration over the energy. The f i(f) (E) in equation (4) are Fermi–Dirac distribution functions. The assumption of Q-independence of H e allows us to reduce equation (4) to a form that provides better insight and is substantially easier to handle numerically. To that end we first separate the vibronic matrix element in equation (4) into interdependent electronic and nuclear factors and introduce a complete set of eigenstates of the ground nuclear Hamiltonian

I ¼ X jv i h v j þ X ð d j n ih n j,

v

n

ð5Þ

where jvi are bound and j n i are incoming wave scattering states of H N . The collective index v denotes the bound-state vibrational indices and n specifies the internal quantum numbers of the free state. With equations (3) and (5), the transition matrix element in equation (4) assumes the form

h v , jH e N j v 0, i¼h j rih rj ih v j X jv ih v j þ X ð d j n ih n j ! h N ðQÞj v 0 i

v

n

h j rih rj ih v jC i,

ð6Þ

where we denote by jC i a superposition of eigenstates of H N :

jC i ¼ X A v j vi þ X ð d A ð nÞj n i,

v

n

ð7Þ

with expansion coefficients A v ¼ hvjh N ðQÞjv 0 i and Að nÞ¼h n jh N ðQÞjv 0 i, deter- mined by the current-triggered excitation event. The physical picture suggested by equations (6) and (7) is simple and general. The rapid electron (hole) scattering event produces a superposition of internally excited states of H N . The discrete state projection of this superposition, the first term on the right-hand side of equation (7), translates into bound-state dynamics;

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vibration, rotation, intermode energy transfer or a surface exchange reaction. The scattering projection of j C i translates into bound–free dynamics, such as desorption or dissociation. Considering first the case of bound–free dynamics, we relate the expansion coefficients in equation (7) to observable probabilities by introducing a set of eigenstates j ni of an asymptotic Hamiltonian H N V N through

ð8Þ

j n i¼j ni þ G N V N j n i:

In equation (8), G N is the Green operator corresponding to the Hamiltonian H N and V N is the potential energy operator in that Hamiltonian. In terms of the asymptotically observed states, equation (7) is written as

j C i ¼ X A v jv i þ X ð d B ð n Þj n i,

v

n

ð9Þ

P n 0 Ð d 0 h nj 0 n 0 iAð 0 n 0 Þ is the amplitude to observe the state j ni at

asymptotically long time. Formally, the B( n) are readily expressed in terms of the

scattering matrix corresponding to H N . Numerically, however, it is more con- venient to solve for the nuclear dynamics in the time domain. As shown for example in [50],

where Bð nÞ ¼

jC ð t Þi ¼ X A v ð t Þj vi þ X ð d A ð nt Þj n i

v

n

¼ X A v ð t Þj vi þ X ð d B ð nt Þj n i,

v

n

ð10Þ

with the initial condition j C ðt ¼ 0Þi ¼ j C i: The information of interest, Bð nÞ ¼ lim t!1 ½e iEt=~ Bð ntÞ ¼ lim t!1 h nj C ðtÞi, is determined by propagating the wave packet on the neutral ground surface to a long time and projecting it on to the j ni. The initial condition jC i is determined by the resonance scattering event and contains the information about the resonance state structure and lifetime. Substituting equations (6) and (9) in equation (4), we express the bound–free reaction rate as

w ð V b ; Þ ¼ ð d P reac ð ; ÞW exc ð , V b ; Þ,

where

P reac ð ; Þ ¼ X j B ð nÞj 2 ¼ X

n

n

lim h nj C ðt Þi

t!1

2

,

W exc ð , V b ; Þ ¼ 2 2 p

~

X

,

f i ð Þ½1 f f ð Þ jh jr i h r j ij 2 ð Þ,

ð11Þ

ð12Þ

ð13Þ

and we indicated explicitly the dependence of the rate on the bias voltage V b and its parametric dependence on the resonance lifetime . Equations (11)–(13) formulate the reaction rate in terms of the current that drives the reaction; W exc ( , V b ; ) is seen to be the resonant component of the transmission rate through the molecular junction, related to the corresponding current as W exc ¼ j/e, e being the electron charge. Thus, the electronic factor in equation (11), W exc ( , V b ; ), describes the rate of excitation of the resonance, while the nuclear

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T. Seideman

factor, P reac ( ; ), is a normalized probability, describing the reaction probability per resonance excitation. Both conceptually and numerically, it is convenient to express equation (13) in terms of projected densities of states as

where

W exc ð , V b ; Þ ¼ 2 2 p ð d f i ð Þ½1 f f ð Þ i ð Þ f ð Þ,

~

i ð E Þ ¼ X jh jr ij 2 ðE Þ

ð14Þ

ð15Þ

is the density of electronic states (DOS) in the initial state, projected on to the resonance orbital, and an analogous expression holds for f (E). The problem of bound–bound dynamics in the nuclear modes is addressed along similar lines, the rate taking a discrete form (section 3.2). Here, however, internal relaxation needs to be taken into account, except in cases where the driving rate can be assumed fast compared with the relaxation rate.

3. Applications In this section, we describe several applications of the theory outlined in section 2. We start in section 3.1 with a discussion of scanning tunnelling microscopy (STM)-triggered reactions. In section 3.2, we turn to the problem of current-induced dynamics in single-molecule transistors.

3.1. Scanning tunnelling microscopy-triggered nanochemistry Two experimental curves of yield versus voltage are shown as symbols in figure 1. Figure 1 (a) shows the results from [51] for desorption of H atoms from H- passivated Si(100) whereas figure 1 (b) gives the data from [52] for desorption of C 6 H 6 from Si(100). The two reactions differ substantially in detail but share several features. Both experiments [51, 52] provide evidence for an electronic mechanism; the large tip–surface distance precludes STM manipulation mechan- isms that rely on the electric field and field gradient at the surface or on chemical contact. The temperature dependence precludes thermal desorption. The sigmoi- dal shape of the voltage dependence in both figure 1 (a) and figure 1 (b) should be noted. These features are common also to the rate versus voltage curves of [53–55], pertaining to the rotation of DCCD on Cu(100) [53], the rotation of CCD on Cu(100) [54], and the displacement of Si adatoms on Si(111)(7 7) [55]. An interesting question in connection with figure 1 (a) is the lifetime of the underlying resonance, this problem being relevant to H-atom nanolithography with a rich variety of proven and projected applications [43–46]. Two remarkable features of figure 1 (b) are the sharp voltage dependence and the large yield observed under mild conditions; under comparable conditions rates about five orders of magnitude lower were reported for the STM-triggered resonance-mediated desorption of CO from a Cu surface [56]. The former question is addressed in section 3.1.1 and the latter in section 3.1.2. We begin this section by exploring the qualitative physics responsible for the features that are general to the STM-driven dynamics of [51–55]. To that end, we first introduce several approximations in equation (14). Given that the tip is remote from the substrate, the coupling of the resonance to the tip continuum can

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Current-driven dynamics in quantum electronics 2399 Figure 1. STM-triggered resonance-mediated desorption. ( a )

Figure 1. STM-triggered resonance-mediated desorption. (a) Desorption of H atoms from Si(100)2 1:H: (.), (m), experimental data of [51]; (—), (– – –), theoretical results of section 3.1.1. (b) Desorption of C 6 H 6 from Si(100): (.), experimental data of [52]; (—) theoretical results of section 3.1.2. The error bars are omitted from both sets of experimental data.

be treated as a perturbations compared with its strong interaction with the substrate continuum. Under these conditions, the projected DOSs in equation (14) can be replaced by those of the uncoupled tip and substrate–adsorbate complex. Subject to the assumption that the resonance is isolated and the DOSs of the tip and the bare substrate are almost constant on the energy scale of the resonance width, the product of DOSs in equation (14) reduces to a Lorentzian function . In the low-temperature limit the Fermi distribution functions are approximated by step functions, with which the integral over is analytically soluble. One finds that

W exc ð , V b ; Þ /

tan

tan

1

1

þ eV b =2

E

F

r

E

F

r

G=2

tan

1

tan

1

E F r =2

E F þ eV b þ r

G

=2

, V b > 0,

, V b < 0,

ð16Þ

where E F is the Fermi energy, r is the resonance energy and G ¼ ~= is the resonance width. The closed-form approximation of equation (16) makes explicit the physical content of the electronic function in equation (11). By contrast with an electron beam, a scanning tunnelling microscopy is a broad-band source of electrons, with an energy band of the order of e|V b | . The excitation function W exc ( , V b ; ) measures the fraction of the current that is transferred via the resonance orbital and is hence available for depositing energy into the vibrational system. Together with equation (16), equation (11) rationalizes the sigmoidal bias dependence of the rate observed experimentally [51–55]. More interestingly,

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it suggests the possibility of extracting resonance lifetimes through fit of equa- tion (11) to experimental data. This invitation is taken up in sections 3.1.1 and 3.1.2 below.

3.1.1. H-atom desorption from Si(100)2 1:H. Electron-energy-loss spectros- copy of Si(100)2 1:H showed a peak with a maximum at 8 eV and an onset at 6 eV [57]. Calculations [58] identified this feature as the ! * transition of the Si H bond, and direct optical excitation experiments with 7.9 eV light [59] confirmed this assignment. The experimental results of [51] shown as full codes and full triangles in figure 1 (a) provide clear evidence for resonance-mediated desorption via the * state of the H–Si complex. Potential energy curves for motion perpendicular to the surface in the ground and the excited * states of H/Si(100) were constructed in [47] based on ab initio electronic structure calculations. These curves are used to compute the energy- resolved probability P reac ( , ) of equation (12) using the method discussed in [60]. Figure 2 shows the probabilities obtained as a function of the electronic-to- vibrational energy transfer and the resonance lifetime . P reac ( , ) is seen to be

lifetime . P r e a c ( , ) is seen to be Figure 2.

Figure 2. Energy-resolved reaction probabilities P reac ð ; Þ of equation (12), for desorp- tion of H atoms from Si(100)2 1:H as a function of the scattering energy E B and the resonance lifetime . (Reproduced with permission from [60].)

Current-driven dynamics in quantum electronics

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Current-driven dynamics in quantum electronics 2401 Figure 3. A schematic illustration of the energetics of a

Figure 3. A schematic illustration of the energetics of a W-tip–Si(100):H-surface junction. Superimposed is the electronic DOS of bulk Si. The position and width of the s ! s resonance, as obtained from a fit of the theoretical results to experimental data (see the text for details), are indicated by the broken curve. We note that the sample work function is 4.91 eV. (Reproduced with permission from [60].)

a narrowly distributed function of the scattering energy E B (E B being the

binding energy), peaked at about zero. As the lifetime increases, the distribution broadens but throughout the range of lifetimes relevant for the H/Si(100) system (vide infra) the desorbate energy distribution remains sharply peaked with width below 0.3 eV. The implications of figure 2 are discussed below. Figure 3 illustrates schematically the energetics of the W-tip–Si:H-surface junction. Since the desorption experiments [43, 45, 47, 51] considered here are performed on H-terminated surfaces, the dangling bonds, which significantly affect

the DOS of the clean Si(100) surface, do not play a role and 0

is better

approximated as the density of unoccupied states of bulk Si than as that of the clean surface. This function, as computed within the density functional theory (DFT), is superimposed on the energy scheme of figure 3. Our results agree with a previous calculation of the bulk Si DOS [61]. The tip DOS is approximated as energy-independent (see [60] for a discussion of the range of validity of this approximation) and the lifetime of the Si H * state is determined by incorporating the dynamic simulation in a least-squares fit loop to the data of [51]. The solid curve of figure 1 (a) gives the numerical desorption yield thus obtained. The lifetime determined is 1.2 fs, essentially independent of the substrate temperature. The H-atom desorption problem is an example of an effectively one- dimensional reaction; excited-state motion is along the ground-state reaction coordinate, the transient excitation event deposits energy into the reaction mode, and intermode energy transfer does not take place. More interesting are multi- dimensional processes, where energy is initially deposited in an internal mode and is subsequently transfered to the reaction mode, owing to efficient mode coupling.

The latter case is exemplified by the C 6 H 6 /Si desorption problem, discussed in the next section.

s

3.1.2. C 6 H 6 desorption from Si(100). The threshold in the yield versus voltage curve of figure 1 (b) coincides to within 0.2–0.3 eV with a sharp peak in the density

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T. Seideman

of electronic states of C 6 H 6 /Si(100), indicating that a localized state is accessed in the STM-triggered tunnelling event. The peak corresponds to the binding energy of a feature observed around 2.3 eV in photoemission studies of benzene/Si(100) and attributed to the highest occupied molecular orbital of the adsorption complex [62]. These observations suggest that the desorption process summarized in figure 1 (b) is mediated by a positive-ion resonance that is predominantly localized on the adsorbate. In [52, 63] the physical considerations involved in the construction of an orthogonal coordinate system and the calculation of ab initio potential energy surfaces for the neutral and ionic states of C 6 H 6 /Si are discussed. Below we provide only a qualitative discussion, assisted by the contour plots of figure 4. Here Z and X are dimensionless coordinates whose mathematical definition [38] is not essential for the present discussion. In terms of physical content, Z takes the role of a desorption coordinate whereas X is a collective mode that accounts for internal

whereas X is a collective mode that accounts for internal Figure 4. ( a ) Neutral

Figure 4. (a) Neutral and (b) ionic potential energy surfaces for C 6 H 6 /Si(100) as obtained within a cluster model at the B3LYP/6-31G** level. Superimposed on the contour plots are the configurations of the stationary states on the surfaces. (Reproduced with permission from [63].)

Current-driven dynamics in quantum electronics

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Current-driven dynamics in quantum electronics 2403 Figure 5. Nuclear dynamics leading to desorption of benzene molecules

Figure 5. Nuclear dynamics leading to desorption of benzene molecules from a Si surface:

expectation values of X (—) and Z (– – –) in the evolving wave packet, subsequent to 25 fs evolution in the ionic state. The inset shows a snapshot of the wave packet 750 fs after relaxation, illustrating highly vibrationally mixed motion in the chemisorption well, some probability density in the physisorption site and a portion of the wave packet propagating along the exit valley. (Reproduced with permission from [64].)

motion; predominantly into-plane motion of the carbon backbone accompanied by relaxation of the Si dimer that supports the ring. The potential energy surfaces of figure 4 are employed to study the nuclear dynamics triggered by the resonance tunnelling process. Figure 5 describes the evolution in the neutral state subsequent to the resonance tunnelling event through plots of the expectation values of X and Z in the wave packet. The initial condition C is determined through 25 fs evolution in the resonant state. Desorption is initiated by large-amplitude vibrational motion across the chemisorption well. Energy initially deposited in the X mode shuttles periodically between the coupled modes for a brief period, after which the oscillation amplitude of hXi decays and desorption is under way, as indicated by a rapid increase in hZi. The inset of figure 5 shows a snapshot of the wave packet at 750 fs, illustrating vibrationally mixed motion in the chemisorption well, some probability density in a weak physisorp- tion site [63], located just beyond the transition state, and a portion of the wave packet propagating along the exit valley. With much shorter residence times (5–20 fs) in the resonance state, the tunnelling event just barely vibrationally excites the system. It undergoes low- amplitude vibrations in the well but remains bound. With much longer times in the charged state (30–40 fs) the system explores highly repulsive regions of the neutral potential energy surface, the amplitude of the short-time vibrational motion in the ring mode grows and desorption is faster [52, 64]. The time-evolving wave packet is employed to extract the energy-resolved desorption probability using the approach of [63]. As was found for the H/Si(100) system in the previous section (see figure 2), P reac ( ; ) for the C 6 H 6 /Si(100) desorption is narrowly distributed. The distribution peaks at around 0 1.2 eV, corresponding to a total desorbate energy 0 E B 0.3 eV. The shift from the

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resonance energy of the threshold in the yield versus voltage curve predicted by equation (16) is thus roughly 0.3 eV, consistent with observation (figure 1 (b)). The solid curve in figure 1 (b) gives the results of a numerical fit of equation (11) to the observed yield. Since our fit is based on a small number of data points, and since the experimental error bars are of the order of the data, determination of a definite lifetime is not appropriate but rough upper and lower bounds can be estimated, 7 fs 9 9 17 fs: Together with figure 4, the relatively long lifetime of the adsorbate-derived C 6 H 6 resonance rationalizes the large yield and the sharp voltage dependence observed for this system. We remark that the ability of a two-dimensional model to capture the dynamics of the many-mode problem is due to features that are specific to the C 6 H 6 /Si(100) system, in particular the near conservation of C 2v symmetry along the reaction pathway. Nonetheless, the rapid nature of the resonance-driven processes envi- saged here is expected more generally to restrict the number of active modes to relatively few. Evolution in the resonant state competes with electronic relaxation and is thus of femto second time scale. Reaction in the neutral state competes with internal relaxation and is thus of a time scale of sub- to a few picoseconds. On such short time scales, a small portion of the resonance-state potential energy surface is explored and, subsequent to electronic relaxation, energy is distributed within a restricted subset of modes.

3.2. Current-triggered dynamics in single-molecule transistors In this section, we apply the theory of section 2 to a particularly simple problem, namely current-induced vibrational excitation of a fullerene adsorbed between two Au contacts. Our choice of a simplest-case-senario model has several motivations. Firstly, an experiment by Park et al. [65] recorded the signature of current-induced vibrational motion in single Au–C 60 –Au transistors. We are not aware of other experimental demonstrations of current-induced dynamics in a molecular device, although we believe that the concept is general 1 . Secondly, the Au–C 60 –Au system offers rich and relatively well-studied [66] electronic dynamics. The ability to control the electronic dynamics, already demonstrated for this system [65, 66] provides potentially a route of manipulating also the nuclear dynamics (vide infra). Thirdly, the nuclear dynamics allow for an analytical approximation which provides useful insight [66]. The molecular device in mind is depicted in figure 6. The Au electrodes extend to electron reservoirs at Z ¼ 1, where the bias voltage V b is applied and electric current is collected. A metal gate with a gate voltage V g is placed near the C 60 molecule, providing a third probe capacitatively coupled to the C 60 . In figure 7 we describe the electronic dynamics of the device of figure 6, as computed within a DFT-based non-equilibrium Green function approach [66]. The inset shows the computed transmission T(E,V b ,V g ) versus the electron energy E at zero bias and gate voltage. The energy scale is set such that E F ¼ 0. T(E,V b ,V g ) is sharply peaked about E 0.15 eV, with a line shape close to the Breit–Wigner form, indicating an isolated resonance and essentially energy- independent direct transmission. This resonance is responsible for the nuclear dynamics. For reference below, we note that its width corresponds to a resonance

1 See Note added in proofs.

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Current-driven dynamics in quantum electronics 2405 Figure 6. Current-triggered dynamics in single-molecule transistors.

Figure 6. Current-triggered dynamics in single-molecule transistors. Schematic diagram of the Au–C 60 –Au molecular device. The Au electrodes extend to Z ¼ 1 where the bias voltage V b is applied. A gate voltage V g may be applied in the scattering region of the device.

g may be applied in the scattering region of the device. Figure 7. Electronic dynamics in

Figure 7. Electronic dynamics in the Au–C 60 –Au device of figure 6 as obtained within a DFT-based non-equilibrium Green function approach. The main diagram shows the excitation function W exc of equation (14) versus the electronic-to-vibrational energy transfer and the bias voltage V b . The inset gives the transmission coefficient TðE,V b, V g Þ versus energy E for zero bias and gate voltages. The transmission peak arises from the resonant orbital that mediates the current-triggered dynamics of figure 8.

lifetime of about 26 fs. At finite bias voltages V b 0, the eigenlevels, and with them the transmission peaks, shift significantly but the overall shape of T(E,V b ,V g ) is only slightly modified. The effect of a finite gate voltage on the transport properties is rather more substantial. By changing the charge distribution in the molecular region and shifting the energy levels, a non-zero gate voltage alters qualitatively both the line centre and the shape of the transmission curve [66]. The main diagram in figure 7 shows the excitation function W exc ( , V b ; ) of equation (14) versus the electronic-to-vibrational energy transfer and the bias voltage V b . We find that the excitation function determined ab initio for a voltage-

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biased molecular transistor follows nicely the form of the analytical approximation of equation (16), namely a sigmoidal function of voltage and energy. This intuitive structure is due to the near-Breit–Wigner shape of the resonance and no longer obtains in devices and energy regimes where resonances overlap. The nuclear dynamics triggered by the electronic transmission of figure 7 are similar in concept to the STM-triggered dynamics of section 3.1. The tunnelling event transiently places the nuclear system in a negative ion state of the Au–C 60 – Au system. Owing to the equilibrium mismatch between the neutral and ionic states, a non-stationary superposition of vibrational eigenstates is formed, which travels towards the ionic state equilibrium while continuously relaxing to the neutral state. Upon electronic relaxation, the population has been redistributed between the vibrational levels of the neutral surface. This qualitative picture is quantified in figure 8. The inset shows the expecta- tion value of z in the neutral state wave packet. We find that the C 60 centre of mass oscillates between the contacts at the fundamental frequency of the neutral surface and an amplitude approximately equal to the distance travelled in the ionic state. Slow damping of the oscillations is due to the anharmonicity of the potential. The main diagram in figure 8 shows the vibrational excitation rate of the Au–C 60 –Au system given by

w v ðV b , Þ ¼ P v ð Þ W exc ð v , V b ; Þ

ð17Þ

(see equations (11) and (12)), as a function of the applied voltage V b and the equilibrium displacement Z eq between the neutral and ion states for v ¼ 1. Our

q between the neutral and ion states for v ¼ 1. Our Figure 8. Rate of

Figure 8. Rate of vibrational excitation of the Au–C 60 –Au device versus bias voltage (see equation (17)). The equilibrium displacement dZ eq between the neutral and ionic states is 1.24 pm ( f ), 4 pm (—), 10 pm ( ), 20 pm (– – –), 25 pm (— — —) and 31 pm (— –—). To allow display on the same scale, the dZ eq ¼ 1:24 pm results are multiplied by a factor of 5. The inset shows the expectation value of Z in the wave packet subsequent to the resonance tunnelling event.

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results correspond to the unmodified molecular junction, V g ¼ 0, and are given for Z eq values covering the physically relevant range; for smaller Z eq the vibrational excitation vanishes whereas for larger values we find a finite desorption probability. The bias-voltage dependence of the w v follows the V b dependence of W exc in equation (17) (see figure 7) and is well approximated by the analytical limit of equation (16), as a result of the isolated nature of the resonance mediating the dynamics. The excitation rates of vibrational levels v > 1 take a similar shape but respond differently to the magnitude of the equilibrium displacement. We find that the essential dynamics are contained in the combination of the equilibrium displacement and the resonance lifetime. The former parameter determines the outcome through the exponential dependence of P reac on Z eq The latter parameter determines the rate through the balance between the dependences of the electronic and nuclear dynamics. Whereas W exc decreases sharply with increasing (see equation (16)), P reac increases (roughly exponen- tially) with this parameter. The ability to manipulate the conductance by varying the distance between the electrodes and the gate voltage thereby translates into control of the current-induced dynamics.

4. Summary and outlook

In the previous sections we reviewed recent theoretical work on the problem of singe-molecule dynamics induced by electric current, a young and exciting field that shares common aspects with several established areas of research, including transport through molecular wires, photochemistry on conducting surfaces, STM manipulation and electron–molecule scattering. Subsequent to a discussion of the qualitative physics underlying current- triggered dynamics in section 1, we outlined a theoretical framework for study of these dynamics (section 2). By introducing an approximation in the form of the electronic Hamiltonian in equation (1), we converted the solution of correlated reactions in the electronic and nuclear modes (equation (4)) into a form that provides better insight and is substantially easier to deal with numerically (equation (11)). In the latter form, the reaction rate is expressed in terms of the

resonant current j ¼ W exc /e that drives the reaction and a normalized reaction probability P reac . The parameters determining the dynamics are spelled out and the computational effort is reduced to that required for a conductance calculation and a reaction dynamics calculation in the nuclear subspace. An analytical approximation of W exc rationalizes a common feature of several experiments, namely the sigmoidal shape of the observed rate versus voltage curves. Application was made to study STM-triggered surface reactions (section 3.1) and current- triggered dynamics in a single-molecule transistor (section 3.2). Clearly, much remains to be done in the area of current-driven dynamics in nanoscale devices. Exploring several of the potential applications proposed in section 1 is one of the topics of ongoing research in our group. In particular, we employ the concepts discussed in section 1.1 to devise a coherently driven unidirectional molecular rotor and a nanoscale rattle, to explore the modification of the conductivity induced by current-triggered torsion in a biphenyl device (section 1.2), and to study the surface proton transfer reaction, NH 3 /Si ! NH 2 / SiþH/Si, mediated by a STM-triggered positive ion resonance of the substrate adsorbate complex (section 1.3).

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Of considerable interest is the development of improved methods for comput- ing the electronic dynamics. Here one seeks approaches that would go beyond the current implementation of DFT, techniques that would economize the calculation and, most importantly, time-domain approaches that would provide better insight into the electronic dynamics. Another exciting avenue that we hope to address is the development of a method that goes beyond the approximation leading to equation (11) by solving simultaneously for the electronic and nuclear dynamics.

Note added in proofs In a recent conference, we became aware of an unpublished experiment by D. Ralph and coworkers, where the signature of current-driven dynamics in mol- ecular transistors was recorded.

Acknowledgments The author is grateful to several postdoctoral fellows and colleagues who contributed to the work reviewed in this article, in particular Dr Saman Alavi, Dr Roger Rousseau and Professor Hong Guo. This work was partially supported by the Natural Science and Engineering Research Council of Canada.

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