Fermi's golden rule rate expression for transitions due to nonadiabatic derivative couplings in the adiabatic basis

TL;DR

This paper derives a comprehensive Fermi's golden rule rate expression for nonadiabatic transitions considering derivative couplings, applicable to complex molecular systems with environmental effects, and demonstrates its utility through azulene decay analysis.

Contribution

It provides a new, general FGR rate expression incorporating nonadiabatic derivative couplings and non-Condon effects, applicable to harmonic oscillator models and molecular decay processes.

Findings

Derived a closed-form FGR rate expression with quadratic NDC contributions.

Included additional bath spectral densities for non-Condon effects.

Applied the theory to azulene nonradiative decay, illustrating practical utility.

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 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 evaluated at the minimum potential energy configuration of the initial adiabatic state as the basis for the zeroth order adiabatic and NDC coupling terms of the Hamiltonian. Although application of this approximation is rather limited, it allows deriving a general FGR rate expression without further approximation and still accounts for non-Condon effect arising from momentum operators of NDC terms and its coupling with vibronic displacements. For a generic and widely used model where all nuclear degrees of freedom and environmental effects are represented as linearly coupled harmonic oscillators, we derive a closed form FGR rate expression that requires only Fourier transform. The resulting rate expression includes quadratic contributions of NDC terms and their couplings to Franck-Condon modes, which require evaluation of two additional bath spectral densities in addition to conventional one that appears in a typical FGR rate theory based on the Condon approximation. Model calculations for the case where nuclear vibrations consist of both a sharp high frequency mode and an Ohmic bath spectral density illustrate new features and implications of the rate expression. We then apply our theoretical expression to the nonradiative decay from the first excited singlet state of azulene, which illustrates the utility and implications of our theoretical results.