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Theoretical approaches to intramolecular electron transfer processes
Author(s) -
Ratner Mark A.
Publication year - 1978
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560140514
Subject(s) - propagator , intramolecular force , formalism (music) , fourier transform , electron transfer , statistical physics , electron , ground state , quantum mechanics , chemistry , physics , computational chemistry , art , musical , visual arts
Theoretical issues that must be considered for calculating rates of intramolecular electron transfer are discussed. The process itself is well defined only if the ground state is well approximated by a localized electronic function (Robin–Day class I or II). Under those conditions, the linear‐response formalism yields the rate as the Fourier transform of the particle–hole propagator. We discuss the validity of electron propagators as approximations to particle‐hole propagators, and find that they are valid, for simple models, within the stability range of the Hartree–Fock procedure. The vibronic nature of the transfer process is stressed, and formal schemes are given for calculating direct and through‐bridge transfer rates. Outstanding difficulties, and applications to biological systems, are very briefly noted.