Abstract
We present a model calculation for the determination of quantum microcanonical average reaction rates for isolated molecules. The model system consists of two coupled electronic states, reactant and product, each with many nuclear motion eigenstates. The reaction rate is evaluated via a resummed perturbation expansion in the electronic coupling. From this we obtain an electronic adiabaticity criterion which depends on the probability to remain at or return to the transition region. We evaluate this survival probability using a global random matrix model for the nuclear Hamiltonian. This leads to an equation for the reaction rate which interpolates between the golden rule electronic crossing rate and the electronically adiabatic rate. We discuss the classical limit and make connection with thermal rate theory.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
