Quantum corrections to classical evaluation of nonadiabatic transition rates

Journal Article · Mon Aug 14 04:00:00 EDT 2006 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2217443· OSTI ID:20864284

Kim, Hyojoon; Rossky, Peter J ^[1]

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1. Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada)

A recently developed quantum correction approach is applied to evaluating the nonadiabatic quantum-mechanical transition rate between Born-Oppenheimer states of a subsystem embedded in a thermal bath of harmonic oscillators. In the first-order perturbation theory, the nonadiabatic rate can be expressed in terms of a quantum-mechanical correlation function, which can be estimated directly from classical data. Application to a popular spin-boson model shows that our results are in excellent agreement with the exact quantum-mechanical results.

• OSTI ID: 20864284
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 125; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
BORN-OPPENHEIMER APPROXIMATION
BOSONS
CORRECTIONS
CORRELATION FUNCTIONS
HARMONIC OSCILLATORS
PERTURBATION THEORY
QUANTUM MECHANICS
SPIN