Year: 2013
Type: article
Abstract: The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing to unfavorable numerical scaling. In this paper we show that this problem can be alleviated by combining it with a formally exact generalized quantum master equation treatment. This allows dramatic improvements in the efficiency of the approach in nonadiabatic regimes, making it computationally tractable to treat the quantum dynamics of complex systems for long times. We demonstrate our approach by applying it to a model of condensed phase charge transfer where our method is shown to be numerically exact in regimes where fewest-switches surface hopping and mean field approaches fail to obtain either the correct rates or long-time populations.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.4812355
Authors: Aaron Kelly, Thomas E. Markland
Institution: Stanford University
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W2134164536