title: Quantum and semiclassical theories for nonadiabatic transitions based on overlap integrals related to fast degrees of freedom.
abstract: Alternative treatments of quantum and semiclassical theories for nonadiabatic dynamics are presented. These treatments require no derivative couplings and instead are based on overlap integrals between eigenstates corresponding to fast degrees of freedom, such as electronic states. Derived from mathematical transformations of the Schrödinger equation, the theories describe nonlocal characteristics of nonadiabatic transitions. The idea that overlap integrals can be used for nonadiabatic transitions stems from an article by Johnson and Levine [Chem. Phys. Lett. 13, 168 (1972)]. Furthermore, overlap integrals in path-integral form have been recently made available by Schmidt and Tully [J. Chem. Phys. 127, 094103 (2007)] to analyze nonadiabatic effects in thermal equilibrium systems. The present paper expands this idea to dynamic problems presented in path-integral form that involve nonadiabatic semiclassical propagators. Applications to one-dimensional nonadiabatic transitions have provided excellent results, thereby verifying the procedure. In principle these theories that are presented can be applied to multidimensional systems, although numerical costs could be quite expensive.
authors.affiliation: Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Komaba, 153-8902, Tokyo, Japan. fujii@tcl.t.u-tokyo.ac.jp
authors.forename: Mikiya
authors.initials: M
authors.lastname: Fujii