Abstract
The authors examine the connection between electron transport under bias in a junction and nonadiabatic intramolecular electron transfer (ET). It is shown that under certain assumptions it is possible to define a stationary current that allows the computation of the intramolecular transfer rate using the same formalism that is employed in the description of transport. They show that the nonequilibrium Green's function formalism of quantum transport can be used to calculate the ET rate. The formal connection between electron transport and electron transfer is made, and they work out the simple case of an electronic level coupled to a vibrational mode representing a thermal bath and show that the result is the same as expected from a Fermi golden rule treatment, and in the high-temperature limit yields the Marcus electron transfer theory. The usefulness of this alternative formulation of rates is discussed.
| Original language | English (US) |
|---|---|
| Article number | 161103 |
| Journal | Journal of Chemical Physics |
| Volume | 126 |
| Issue number | 16 |
| DOIs | |
| State | Published - 2007 |
Funding
The authors thank Michael Galperin, Abraham Nitzan, and Robert Cave for helpful discussions. One of the authors (S.Y.) is grateful for support from the Office of Naval Research through a NDSEG fellowship. Funding was provided by the NSF/MRSEC program and by the MURI/DURINT program of the DoD.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry