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A generalized quantum master equation approach is introduced to describe electron transfer in molecular junctions that spans both the off-resonant (tunneling) and resonant (hopping) transport regimes. The model builds on prior insights from scattering theory but is not limited to a certain parameter range with regard to the strength of the molecule–electrode coupling. The framework is used to study the simplest case of energy and charge transfer between the molecule and the electrodes for a single site noninteracting Anderson model in the limit of symmetric and asymmetric coupling between the molecule and the electrodes. In the limit of elastic transport, the Landauer result is recovered for the current by invoking a single active electron Ansatz and a binary collision approximation for the memory kernel. Inelastic transport is considered by allowing the excitation of electron–hole pairs in the electrodes in tandem with charge transport. In the case of low bias voltages where the Fermi levels of the electrodes remain below the molecular state, it is shown that the current arises from tunneling and the molecule remains neutral. However, once the threshold is reached for aligning the fermi level of one electrode with the molecular orbital, a small amount of charge transfer occurs with a negligible amount of hopping current. While inelasticity in the current has a minimal impact on the shape of the current–voltage curve in the case of symmetric electrode coupling, the results for a slight asymmetry in coupling demonstrate complete charge transfer and a significant drop in current. These results provide encouraging confirmation that the framework can describe charge transport across a wide range of electrode–molecule coupling and provide a unique perspective for developing new master equation treatments for energy and charge transport in molecular junctions. An extension of this work to account for inelastic scattering from electron–vibrational coupling at the molecule is straightforward and will be the subject of subsequent work.
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Coherent and incoherent contributions to molecular electron transport
We numerically isolate the limits of validity of the Landauer approximation to describe charge transport along molecular junctions in condensed phase environments. To do so, we contrast Landauer with exact time-dependent non-equilibrium Green’s function quantum transport computations in a two-site molecular junction subject to exponentially correlated noise. Under resonant transport conditions, we find Landauer accuracy to critically depend on intramolecular interactions. By contrast, under nonresonant conditions, the emergence of incoherent transport routes that go beyond Landauer depends on charging and discharging processes at the electrode–molecule interface. In both cases, decreasing the rate of charge exchange between the electrodes and molecule and increasing the interaction strength with the thermal environment cause Landauer to become less accurate. The results are interpreted from a time-dependent perspective where the noise prevents the junction from achieving steady-state and from a fully quantum perspective where the environment introduces dephasing in the dynamics. Using these results, we analyze why the Landauer approach is so useful to understand experiments, isolate regimes where it fails, and propose schemes to chemically manipulate the degree of transport coherence.
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- PAR ID:
- 10363527
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 156
- Issue:
- 9
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- Article No. 094302
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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