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Semiclassical initial value representation for the quantum propagator in the Heisenberg interaction representation

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4936922· OSTI ID:22493307
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  1. Chemical Physics Department, Weizmann Institute of Science, 76100 Rehovot (Israel)
One of the challenges facing on-the-fly ab initio semiclassical time evolution is the large expense needed to converge the computation. In this paper, we suggest that a significant saving in computational effort may be achieved by employing a semiclassical initial value representation (SCIVR) of the quantum propagator based on the Heisenberg interaction representation. We formulate and test numerically a modification and simplification of the previous semiclassical interaction representation of Shao and Makri [J. Chem. Phys. 113, 3681 (2000)]. The formulation is based on the wavefunction form of the semiclassical propagation instead of the operator form, and so is simpler and cheaper to implement. The semiclassical interaction representation has the advantage that the phase and prefactor vary relatively slowly as compared to the “standard” SCIVR methods. This improves its convergence properties significantly. Using a one-dimensional model system, the approximation is compared with Herman-Kluk’s frozen Gaussian and Heller’s thawed Gaussian approximations. The convergence properties of the interaction representation approach are shown to be favorable and indicate that the interaction representation is a viable way of incorporating on-the-fly force field information within a semiclassical framework.
OSTI ID:
22493307
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English