An accurate, non-empirical method for incorporating decoherence into Ehrenfest dynamics

Esch, Michael P.; Levine, Benjamin G

doi:10.1063/5.0070686

An accurate, non-empirical method for incorporating decoherence into Ehrenfest dynamics

Journal Article · Tue Nov 30 23:00:00 EST 2021 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0070686· OSTI ID:1978978

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State University of New York (SUNY), Stony Brook, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
State University of New York (SUNY), Stony Brook, NY (United States)

In mixed quantum-classical nonadiabatic molecular dynamics methods, the anchoring of the electronic wave function to a single nuclear geometry results in both quantitative and qualitative errors in the dynamics. In the context of both Ehrenfest and trajectory surface hopping methods, methods for incorporating decoherence are widely used to eliminate these errors. However, the accuracy of these methods often depends strongly on the parameterization of the decoherence time and/or other related quantities. Here, we present a refinement of the recently introduced collapse to a block (TAB) scheme for incorporating decoherence into Ehrenfest dynamics. The proposed approach incorporates an approximation to the history of the population dynamics and treats the coherence decay as Gaussian, rather than exponential. This method uses parameters that can be obtained from first principles, rather than empirical fitting. Application to one-dimensional models indicates excellent agreement with numerically exact simulations. We also introduce a second refinement to the TAB method: a robust linear least-squares algorithm for determining collapse probabilities.

View Accepted Manuscript (DOE)

Research Organization:: State University of New York (SUNY), Albany, NY (United States); State University of New York (SUNY), Stony Brook, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Stony Brook University

Grant/Contract Number:: SC0021643

OSTI ID:: 1978978

Alternate ID(s):: OSTI ID: 1833461

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 21 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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An accurate, non-empirical method for incorporating decoherence into Ehrenfest dynamics

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