LETTER pubs.acs.

org/NanoLett

Novel Quantum Interference Effects in Transport through Molecular Radicals

Justin P. Bergeld,*, Gemma C. Solomon, Charles A. Staord, and Mark A. Ratner||

Departments of Chemistry and Physics, University of California, Irvine, California 92697, United States Nano-Science Center and Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen , Denmark Department of Physics, University of Arizona, 1118 East Fourth Street, Tucson, Arizona 85721, United States Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
S b Supporting Information

ABSTRACT: We investigate electronic transport through molecular radicals and predict a correlation-induced transmission node arising from destructive interference between transport contributions from dierent charge states of the molecule. This quantum interference eect has no single-particle analog and cannot be described by eective single-particle theories. Large errors in the thermoelectric properties and nonlinear currentvoltage response of molecular radical junctions are introduced when the complementary wave and particle aspects of the electron are not properly treated. A method to accurately calculate the low-energy transport through a radical-based junction using an Anderson model is given. KEYWORDS: Quantum transport, molecular radicals, DFT, many-body, Mott-node

he vast majority of calculations of electronic transport through single molecules strongly bound to electrodes assume that the process occurs via the tunneling of phase coherent electron waves with the neutral ground electronic state of the system describing the entirety of the process. However, the very nature of charge transport, whereby individual electrons tunnel (virtually) onto and o of the molecule, suggests that this may not be a complete physical description. Here we investigate electronic transport in radical-based single-molecule junctions (SMJs) and predict a new type of transmission node arising from interferences between transport pathways involving dierent charge states of the molecule, requiring that the complementary wavelike and particle-like nature of the electron be treated simultaneously. Such Mott nodes are independent of junction topology and are predicted to occur in the experimentally relevant transport regime of all molecular radical-based junctions. As an example, we consider transport through a AupentadienyldithiolAu SMJ, shown schematically in Figure 1. The simulated transmission spectra and molecular charge imbalance for the -electrons of this radical-based junction are shown as a function of the leads chemical potential in Figure 2. The transport was calculated using a many-body theory based on the molecular Dyson equation (MDE), which includes all states of the isolated radical exactly.1 These calculations utilize a basis of frozen nuclei since we focus on transport in the cotunelling regime, where structural relaxation is not expected to be signicant. Image charge eects2 from the nearby metal electrodes are not included in the calculations because they have no signicant
r 2011 American Chemical Society

Figure 1. A schematic diagram of the AupentadienyldithiolAu junction we use as an example throughout this article.

eect on the Mott node. All simulations presented here are for junctions operating at room temperature where we assume phase coherent transport. The eect of dephasing is discussed in the Supporting Information. When is commensurate with the molecular midgap energy 0,3 the transmission spectrum exhibits a node, a spectral feature indicative of interference.410 However, the origin of this node is not the specic molecular topology, since the pentadienyl radical is a linear molecule whose -orbital electronic system lacks any topological nodes. Instead, this Mott node is a manifestation of complete destructive interference between the transmission amplitudes for electrons and holes, quantities involving dierent charge
Received: March 28, 2011 Revised: May 24, 2011 Published: June 10, 2011
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Figure 2. The transmission probability T(E) for both spin species (R and ) and the average molecular charge imbalance Q/e are shown near the HOMO and LUMO resonances11 of a pentadienyldithiol radical SMJ as a function of lead chemical potential . Both spins contribute equally to the transport since there is no broken spinsymmetry.12 The spectrum encompasses three charge states (1,0,1) of the molecule and exhibits both Coulomb blockade peaks and a midgap node when = 0. This Mott-node stems from quantum interferences between transmission amplitudes involving dierent charge states of the molecule. Calculations were performed using MDE theory1 for the -orbitals of a SMJ operating at room temperature with a symmetric lead-molecule coupling = 0.5 eV. e is the electrons charge.

Figure 3. The electronic transmission spectrum for the R and spins of a AupentadienyldithiolAu radical junction calculated using spinunrestricted DFT. The midgap energy 0 was chosen as the energy origin rather than the Fermi energy of gold in order to be consistent with the MDE calculations.

states of the molecule. When = 0 these amplitudes cancel, giving rise to a node, whereas when < 0 or > 0 the transport is dominated by holes or electrons, respectively, and the destructive interference between the amplitudes is not complete. Fundamentally, a description of this type of interference requires a transport theory that correctly accounts both for the charge uctuations of the system and quantum coherence, since the splitting of the transmission amplitude poles is a particle eect (Coulomb blockade) while their interference is a quantum wave eect. Electronic transport calculations involving molecules often utilize eective single-particle spin-unrestricted methods, such as unrestricted HartreeFock (UHF) or an implementation of density functional theory (DFT), where the molecular orbitals for each spin are solved independently, leading to states with broken spin-rotation symmetry. This allows for a better description of the molecular energy spectrum, particularly for the case of molecular radicals, where spin-restricted methods fail to describe a HOMOLUMO gap. However, transport depends not only on energy levels but also on the matrix elements between the initial and nal states of the system. Because of the discrete nature of the charges being transported, these matrix elements involve dierent charge states of the molecule and require a many-body theory for their proper description. An alternative computational approach to the transport problem is to solve the few-body molecular Hamiltonian exactly and to treat electron hopping between molecule and electrodes as a perturbation. This approach was initially used to describe molecular junction transport in the sequential-tunneling regime.1315 Higher-order tunneling processes may be included in the density-matrix formalism16,17 and the closely related superoperator Greens function approach,1820 where the expansion is typically truncated at second19 or fourth order.16,21 Here, we utilize a MDE theory1 based on ordinary nonequilibrium Greens functions (NEGFs), which allows for the inclusion of tunneling

processes to all orders for each class of diagram. We emphasize, however, that any transport theory that properly accounts for the complementary wave-particle nature of the electron should exhibit Mott nodes. Currently, most modern transport calculations involve implementations of DFT, a theory that would give the exact electronic ground state if the exact exchange-correlation functional were known. A spin-unrestricted DFT calculation of the transmission through a pentadienyl radical SMJ is shown in Figure 3, where no transmission nodes are found. Despite DFTs sophistication, existing implementations of the exchange-correlation functional do not properly describe the quantization of charge14,2224 and consequently the resulting transport does not exhibit a Mott node. The thermopower spectrum of a pentadienyl radical SMJ calculated using both MDE and DFT is shown in Figure 4. In the MDE simulation, the eect of tunneling through -orbitals was included by adding a phenomenological constant T = 1.27 105 to the transmission probability, where T = ANeN and the values AN = 0.0006, N = 0.77 and N = 5 are consistent with the thiol end-groups of the pentadienyl SMJ.2527 In the limit that T = 0, the thermopower reaches a maximum value of 156 V/K.9 The peak thermopowers found using MDE and DFT were 42 and 7 V/K, respectively. Since the thermoelectric response is enhanced near transmission nodes9,10 and MDE theory predicts a midgap node while DFT does not, the peak thermopower predicted by the former is larger than the latter. This enhancement is a clear experimental signature of Mott nodes. In order to investigate the nature of the Mott node it is necessary to consider transport theory in some detail. The transmission function of a junction T(E) can be used to compactly express a number of important linear-response transport quantities9 such as the zero-bias conductance G e2 L and the thermopower S where L
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1 L eT L

1 0

1 h

  Df dEE TE DE

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broadened and imbued with nite lifetimes. Using the molecular Dyson equation1 the full Greens function of the SMJ may then be written in terms of Gmol as GE Gmol E Gmol EEGE (0). C 9 Gmol is found by where = T C and C = C exact diagonalization of Hmol, including all charge states and excited states of the molecule, and the correction to the Coulomb self-energy C is found using NEGF methods.1 We consider transport in the elastic cotunneling approximation1 where C = 0. In the basis of exact eigenstates of the molecular Hamiltonian Gmol is given by1 Gmol E

Figure 4. The thermopower S of a AupentadienyldithiolAu SMJ is shown near the midgap energy 0 calculated using MDE and spinunrestricted DFT. The peak thermopowers Speak found using MDE and DFT were 42 and 7 V/K, respectively. In the MDE simulation, the eect of tunneling through -orbitals was included by adding a phenomenological constant T = 1.27 105 to the -orbital transmission probability.2527 Neglecting tunneling through -orbitals, Speak = 156 V/K near the midgap node. The atomic positions used in both the MDE and DFT calculations were identical. The thermopower is independent of the lead-molecule coupling .

P P 0 C, 0 E E0 E i0 0

10

where and 0 label eigenstates of Hmol and P () is the probability that state is occupied. In linear-response, P () = e(EN)/Z , where Z =e(EN) is the grand canonical partition function. The many-body matrix element
C, 0 n, m0 jdn j0 0 jdm0 j

In the elastic transport regime, the nonlinear current through a two-terminal junction can also be expressed in terms of the transmission function28 Z e I TEf2 E f1 E 4 h where f(E) = {1 exp[(E )]}1 is the FermiDirac distribution for lead at inverse temperature = 1/kBT. From eqs 14, it is clear that any errors in T(E) lead directly to errors in observable transport quantities. The elastic transmission function for a two-terminal junction is given by29 TE TrfL EGER EG Eg 5 where (E) is the tunneling-width matrix for lead and the trace includes spin. The retarded Greens function G(E) of the junction may be written as GE SE Hmol E1 Hmol=H(1) mol H(2) mol
1

11

where dn (d ) annihilates (creates) an electron with spin on n the nth atomic orbital of the molecule and and 0 label molecular eigenstates with dierent charge occupancies. In eective single-particle theories, such as UHF and current implementations of DFT, many-body interactions are treated approximately, resulting in a static energy shift of the one-body ~ mol ~ mol ~ ~ energies E, where H(1) (E) f H (1) and H (1) | = E|. mol The molecular Greens function in this case is given by ~ 1 Gmol E SE Hmol i0 1 12

is the molecular Hamiltonian (see where Supporting Information) which we formally separate into onebody and two-body terms. S is an overlap matrix, which in an orthonormal basis reduces to the identity matrix, and E L E R E C E T T 7 is the self-energy, including the eect of both a nite leadmolecule coupling via L,R and many-body interactions via the T Coulomb self-energy C(E). The tunneling self-energy matrices are related to the tunneling-width matrices by (E) [ (E)] = T T i(E). It is advantageous to dene a molecular Greens function Gmol(E) = limf0G(E). In the sequential tunneling regime,1 where lead-molecule coherence can be neglected, the molecular Greens function within MDE theory is given by Gmol E SE Hmol C E1 H(1) mol
1 0

Although a junctions Greens function is generally too complicated to work with analytically, the low-energy excitation spectrum most relevant experimentally of a molecular radical (i.e., the region between the HOMO and LUMO resonances11) is typically dominated by the unpaired electron. This allows us to map the molecular problem onto a simpler Anderson model to a very good approximation with two parameters: the eective lead~ molecule coupling and charging energy U. In what follows, we investigate the Anderson mapping of the pentadienyl radical SMJ using UHF and MDE and nd that the Anderson mapping of this junction is extremely accurate, quantitatively reproducing the low-energy spectrum of the full junction. An Anderson molecule has the following Hamiltonian30 Hmol v nv V nV Unv nV 13 where n = d d is the number operator for spin and U is the charging energy. The occupancy of an Anderson molecule can vary between zero and two, where a natural many-body eigenbasis is the set of Fock states {|0,|v,|V,|vV} with corresponding eigenenergies {0, v, V, v V U}. The Anderson junction therefore has two electronic addition resonances for each spin species : one at and another at U. In mapping the full h molecular spectrum onto an Anderson model the two free ~ parameters and U are chosen to produce the correct resonance widths and HOMOLUMO gap, respectively. A similar mapping is discussed in ref 31. The solution of the Anderson model provides a paradigm to describe Coulomb blockade and the Kondo eect in quantum dots and SMJs.32 For temperatures less than the Kondo
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and the Coulomb where all one-body terms are included in self-energy (0) accounts for the eect of all two-body intramolecular many-body correlations exactly. In the presence of nite lead-molecule coupling 6 0 and the molecular states are

Nano Letters temperature TK the Mott node will be lled in by spin-ip tunneling processes. Using parameters found from the MDE simulation of the pentadienyl radical SMJ TK 5 105K at the center of the HOMOLUMO gap (see Supporting Information), indicating that there will be little or no observable eect at room temperature for this junction. The MDE molecular Greens function for spin may be derived from the molecular Hamiltonian eq 13 using eq 10 giving33 Gmol E 1 n n E i0 E U i0 14

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where the bar on the spin index indicates the opposite spin and the thermodynamic factors P () and P (0 ) have been rewritten in terms of the average occupancy of spin h U 2 e e 15 n Z The eective parameters needed to map the many-body molecular problem onto an Anderson model are given by ~ Trf C, 0 g and U LUMO HOMO E(0) N1 E(0), N E(0) N E(0) , N1 17 E(0) N where LUMO = HOMO = and is the ground state energy of the neutral molecule. Note that without any broken spin-symmetry (i.e., with v = V) each spin species molecular Greens function has two poles, a consequence of the fact that there are two nonzero many-body matrix elements: |d |0 and vV|d |. h In order to understand why the Mott node is not predicted by eective single-particle theories, we consider the molecular Greens function in the UHF approximation, where eq 13 be~ ~ ~ mol comes H (1) = HUHF = En, with E = Un . In eective mol single-particle theories like UHF, particles interact with the static potential arising from the average potential made by the other particles. Using eq 12 with an orthonormal basis, the molecular Greens function for spin in the UHF approximation is given by GUHF E mol 1 E Un i0 18 16

Figure 5. The transmission spectrum of a pentadienyl radical SMJ calculated using MDE and the spectra of an Anderson model of the same junction calculated using MDE and UHF. Compared with the full MDE transmission spectrum, the Anderson MDE spectrum has a maximal absolute error of 105 in the midgap region. All transmission nodes in these spectra are Mott nodes; no topological paths exist in either the full pentadienyl molecule or in the Anderson molecule. Inset: The transmission function in the vicinity of the HOMO resonance showing that the UHF peak height is half the MDE peak height. In these calculations = ~ 0.5 eV, = 0.1225 eV and U = 5.85 eV.

which consists of only a single pole per spin species. The spacing ~ between the individual poles for up and down spins is E = U|nv nV|, which matches the spacing of the two poles in eq 14 when n = 1 and spin-rotation symmetry is maximally broken. UHF uses a spin-gap in the spectrum of an eective single-particle Hamiltonian to mimic a charge gap in the spectrum of the true interacting Hamiltonian. The transmission spectrum of a pentadienyl radical SMJ calculated using MDE and the spectra of an Anderson model of the same junction calculated using MDE and UHF are shown ~ as a function of chemical potential in Figure 5. Here = 0.1225 eV and U = 5.85 eV. All transmission nodes exhibited in these spectra are Mott nodes; no topological paths exist through the -orbitals of either the full pentadienyl radical or the Anderson molecule that produce such nodes. From the gure, we see that the many-body treatment of the Anderson model accurately reproduces the low-energy spectrum of the full MDE calculation including the Mott node, although only two of the ten total resonances are included. In contrast, the UHF solution of

Figure 6. The current as a function of bias voltage for an Anderson junction using MDE and UHF. Each theory predicts steps in the current at the same voltages, but the heights of the two steps are dierent. For voltages between the two current steps, MDE predicts a plateau height of two-thirds while the spin-unrestricted approach gives one-half.

the Anderson model fails to predict the midgap Mott node, even though the resonance energies are correct. There is also a peak height discrepancy, shown in the inset of the same gure, where the UHF peak heights are only 50% of those found using MDE. With the analytic form of the molecular Greens functions we can investigate the origin of the Mott node in the Anderson junction directly, since whenever Gmol(0) = 0 then T(0) = 0. The molecular Greens function eq 14 has two poles, corresponding to a hole-excitation and an electron-excitation. When = 0, the numerator of each pole is the same but the denominators have opposite signs, giving rise to a Mott node. In contrast, the UHF molecular Greens function eq 17 neglects the dierent charge states of the molecule and possesses only a single pole per spin species and, consequently, neglects the particle-hole interference which produces the Mott node. The reduced number of poles in the UHF Greens function is also the reason for the 50% transmission peak height reduction, since only half as many poles
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Nano Letters contribute on resonance as compared to the many-body MDE Greens function. The nonlinear current through a pentadienyl radical SMJ, described by the corresponding Anderson model, is shown as a function of bias voltage in Figure 6, using both the MDE and UHF Greens functions. The Coulomb staircase was calculated ~ using eq 4 and has been normalized in units of e/p to highlight the relative step height found in each theory. A current step occurs at a voltage V where the leads chemical potentials correspond to molecular addition energies, opening an additional transport channel of the junction. In the simulations, the equilibrium chemical potential 0 = 5 eV, the charging energy U = 5.85 eV and = 3 eV such that the rst step occurs at V = 2 V and the second 2U away at V = 13.7 V. As the gure shows, each theory predicts steps in the current at the same voltages, although the heights of the two steps are dierent. For voltages between the two current steps, only two charge states of the junction are energetically accessible, and the many-body theory predicts a plateau height of two-thirds while the spin-unrestricted approach gives one-half. The inability of mean-eld theories to correctly describe the relative step heights in the currentvoltage curve of a SMJ in the Coulomb blockade regime has been put forward as a smoking gun for the importance of many-body correlations.14 In UHF theory, Gmol has only a single pole per spin species, meaning that both step heights of the Coulomb staircase of the Anderson model are identical (one-half in normalized units) since when V = 2 V the spin-up-only channel opens and when V = 13.7 V the spin-down-only channel opens. In contrast, the MDE Gmol has two poles per spin species so when V = 2 V a charge channel opens transporting electrons of both spins. But when V = 13.7 V the step is reduced since, according to the Pauli-exclusion principle, only one spin-channel is available.34 The rst current step height is therefore twice as high as the second giving two-thirds and one-third in normalized units, respectively. The incorrect pole structure of the UHF Greens function is a direct consequence of the spin-unrestricted mean-eld theory used in deriving it. As weve seen, approximations inherent to such theories give rise to a qualitatively incorrect transmission function and lead to signicant errors in the thermoelectric properties and nonlinear currentvoltage curves of radical-based molecular junctions. However, by mapping the full radical problem onto the much simpler Anderson model and evaluating that model using a many-body theory, the transport can be accurately described in the low-energy regime most relevant experimentally. In conclusion, we predict the existence of Mott nodes, correlation-induced spectral features arising from interferences between transport pathways involving dierent charge states of the molecule. These nodes do not stem from the topology of a junction; even linear molecules and molecules without any internal structure, such as the Anderson molecule, exhibit them provided there is on average an unpaired electron on the molecule. Eective single-particle theories like UHF and DFT are known to accurately describe the wavelike nature of the electron in SMJ transport. However, they fail to describe the Coulomb blockade regime3538 where the electric charge on the junction is quantized. Fundamentally, Mott nodes require that the Coulomb blockade and coherent tunneling transport regimes be treated simultaneously, since they are a consequence of quantum coherence between dierent molecular charge states. In addition to being an interesting interference phenomenon, such nodes can also serve as a litmus test for any many-body transport theory, since their

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prediction necessitates that the particle-like and wavelike nature of the electron be treated on an equal footing.

ASSOCIATED CONTENT
S b

Supporting Information. Includes a discussion of the model Hamiltonian used in the MDE calculations, the Kondo temperature and the eect of dephasing on the Mott-node. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author

*E-mail: jberge@uci.edu.

ACKNOWLEDGMENT The authors wish to thank Carmen Herrmann for useful discussions. The research leading to these results has received funding from the European Research Council under the European Unions Seventh Framework Programme (FP7/ 2007-2013)/ERC Grant 258806. This work was supported by the Nonequilibrium Energy Research Center (NERC) which is an Energy Frontier Research Center funded by the U.S. Department of Energy, Oce of Science, Oce of Basic Energy Sciences under Award Number DE-SC0000989. REFERENCES
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