Low temperature electron transfer in strongly condensed phase

Details Low temperature electron transfer in strongly condensed phase Low temperature electron transfer in strongly condensed phase

2003-08-16

arxiv.org/abs/cond-mat/0308326v2

Physics

Condensed Matter

Statistical Mechanics

16 pages, 6 figures, revised version with minor changes

Scientific paper

10.1063/1.1630297

Electron transfer coupled to a collective vibronic degree of freedom is studied in strongly condensed phase and at lower temperatures where quantum fluctuations are essential. Based on an exact representation of the reduced density matrix of the electronic+reaction coordinate compound in terms of path integrals, recent findings on the overdamped limit in quantum dissipative systems are employed. This allows to give for the first time a consistent generalization of the well-known Zusman equations to the quantum domain. Detailed conditions for the range of validity are specified. Using the Wigner transform these results are also extended to the quantum dynamics in full phase space. As an important application electronic transfer rates are derived that comprise adiabatic and nonadiabatic processes in the low temperature regime including nuclear tunneling. Accurate agreement with precise quantum Monte Carlo data is observed.

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