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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0070686· OSTI ID:1978978
 [1];  [2]
  1. State University of New York (SUNY), Stony Brook, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
  2. State University of New York (SUNY), Stony Brook, NY (United States)
+ Show Author Affiliations
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.
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:
Stony Brook University; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
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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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Ehrenfest dynamics
molecular dynamics
quantum chemical dynamics
surface hopping