Fermi's Golden Rule Rate Expression for Transitions Due to Nonadiabatic Derivative Couplings in the Adiabatic Basis.

ABSTRACT: Starting from a general molecular Hamiltonian expressed in the basis of adiabatic electronic and nuclear position states, where a compact and complete expression for the nonadiabatic derivative coupling (NDC) Hamiltonian term is obtained, we provide a general analysis of the Fermi's golden rule (FGR) rate expression for nonadiabatic transitions between adiabatic states. We then consider a quasi-adiabatic approximation that uses crude adiabatic states and NDC couplings, both evaluated at the minimum potential energy configuration of the initial adiabatic state, for the definition of the zeroth and first-order terms of the Hamiltonian. Although the application of this approximation is rather limited, it allows deriving a general FGR rate expression without further approximation while account

SUBMITTER: Jang SJ 

PROVIDER: S-EPMC11866763 | biostudies-literature | 2025 Feb

REPOSITORIES: biostudies-literature