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Physics Letters A

Derivation of a quantum time autocorrelation function from a classical white-noise process

Santiago Velasco, Juan A. White

Published Jun 1, 1990• 3 citations
Publisher
DOI
10.1016/0375-9601(90)90960-v

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Two different approaches (quantum and semiclassical) used to calculate time-dependent transition rates for a multilevel molecular system stochastically interacting with a thermal bath are presented. While the former is based on the use of a relationship between the real and the imaginary parts of the time autocorrelation function (TAF) associated with the interaction Hamiltonian, the latter relies on the replacement of a quantum TAF by the corresponding anticommutator. Two well-known examples for a stochastic interaction Hamiltonian, an Ornstein-Uhlenbeck process and a white-noise process, have been considered. In both cases, explicit expressions for the transition rates in terms of a reduced set of parameters characterizing the bath are obtained. In the Gaussian regime both quantum and semiclassical transition rates show a time-damped oscillatory behavior towards the same steady value. In the white-noise (\ensuremath{\delta}-correlated) regime, while the quantum transition rates are time dependent, the semiclassical rates are not. The high- and the low-temperature limits for the quantum and the semiclassical transition rates are also reported. The semiclassical results reduce to the quantum results only in the high-temperature limit.