Dynamics of radiationless transitions in large molecular systems:A Franck-Condon-based method accounting for displacements and rotations of all the normal coordiantes

摘要

An efficient method to study the dynamics of radiationless transition in large molecular systems is proposed.It is based on the use of the whole set of normal coordintes of vibration adn allows for taking properly into account both the displacements and the mix of the normal modes upon transition between two electronic states.the Hamiltonian matrix elements are written in terms of generalized Franck-Condon integrals and are analytically evaluated by recursion formulas.Applications to the S_2->S_1 internal conversion in pyrazine and to long-range electron transfer between quinones in photosynthetic reaction centers are given.