Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 131, Issue 3, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.3176509
Keywords
charge exchange; friction; Liouville equation; reaction kinetics theory
Funding
- National Natural Science Foundation of China [20733006, 20873157]
- Chinese Academy of Sciences [KJCX2.YW.H17]
- National Science Foundation [CHE-0809506]
- Direct For Mathematical & Physical Scien [0809506] Funding Source: National Science Foundation
- Division Of Chemistry [0809506] Funding Source: National Science Foundation
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Electron transfer is investigated at the limit of strong friction. The analysis is based on the generic model of a two-state system bilinearly coupled to a harmonic bath. The dynamics is described within the framework of the mixed quantum classical Liouville (MQCL) equation, which is known to be exact for this model. In the case of zero electronic coupling, it is shown that while the dynamics of the electronic populations can be described by a Markovian quantum Smoluchowski equation, that of the electronic coherences are inherently non-Markovian. A non-Markovian modified Zusman equation is derived in the presence of electronic coupling and shown to be self-consistent in cases where the standard Zusman equation is not.
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