Multilevel Redfield treatment of bridge-mediated long-range electron transfer. A mechanism for anomalous distance dependence
- Columbia Univ., New York, NY (United States)
The density matrix formalism is used to consider long-range electron transfer through a delocalized bridge system that is dissipatively coupled to a thermal bath. Under conditions when the bridge is weakly populated, a distance-independent transfer mechanism arises that eventually dominates the exponentially distance-dependent nonadiabatic tunneling process typically observed. This model offers a possible explanation for the anomalously rapid long-range photoelectron transfer recently observed by Barton and Turro et al, for donor and acceptor species intercalated into a DNA double helix. Predicted electron-transfer rates are obtained by numerically solving the Redfield equation for the density matrix of the full donor-bridge-acceptor system in the presence of stochastic fluctuations induced by the bath. 43 refs., 17 figs., 4 tabs.
- DOE Contract Number:
- FG02-90ER14162
- OSTI ID:
- 6758773
- Journal Information:
- Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 99:9; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
Similar Records
Bridge-assisted electron transfer: Effective electronic coupling
Related Subjects
400201 -- Chemical & Physicochemical Properties
550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
661100 -- Classical & Quantum Mechanics-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
CHEMICAL REACTIONS
DATA
DISTANCE
DNA
ELECTRON DENSITY
ELECTRON TRANSFER
INFORMATION
MATHEMATICAL MODELS
MECHANICS
NUCLEIC ACIDS
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
QUANTUM MECHANICS