Quantum equilibrium structure for strong nonadiabatic coupling: Reaction rate enhancement

Publication Type:

Journal Article

Authors:

Source:

Chemical Physics Letters, Volume 440, Number 4-6, p.215-220 (2007)

URL:

https://www.scopus.com/inward/record.uri?eid=2-s2.0-34248680749&doi=10.1016%2fj.cplett.2007.04.039&partnerID=40&md5=95de3b7e34c24e0cb399004ce9696b9d

Keywords:

Correlation methods, Excited states, Ground state, Liouville dynamics, Nonadiabatic coupling, Quantum equilibrium, Quantum Theory, Reaction rates

Abstract:

The quantum reactive flux correlation function is computed for a two-level system using an expression for the quantum equilibrium structure appropriate for strong nonadiabatic coupling, in conjunction with quantum-classical Liouville dynamics. The magnitude of the quantum mechanical enhancement of the reaction rate as a result of strong nonadiabatic coupling is studied. The reaction rate is found to increase strongly with an increase in the nonadiabatic coupling strength as well as with a decrease in the temperature. Equilibrium quantum effects increase the ground-state contribution to the rate constant but these effects decrease the excited-state contribution. © 2007 Elsevier B.V. All rights reserved.

File Attachment:

mqc-kim-cluster-cpc-08.pdf