Journal
CHEMICAL PHYSICS
Volume 482, Issue -, Pages 124-134Publisher
ELSEVIER
DOI: 10.1016/j.chemphys.2016.09.036
Keywords
Vibronic spectra; Ring-polymer molecular dynamics; Nonadiabatic; Mapping approach
Funding
- Alexander von Humboldt Foundation
- European Union COFUND/Durham Junior Research Fellowship
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Nonadiabatic ring-polymer molecular dynamics employs the mapping approach to describe nonadiabatic effects within the ring-polymer ansatz. In this paper, it is generalized to allow for the nuclear and electronic degrees of freedom to be described by different numbers of ring-polymer beads. Analysis of the resulting method shows that as the number of electronic mapping variables increases, certain problems associated with the approach are removed, such as the non-unique choice of the mapping Hamiltonian and negative populations leading to inverted potential-energy surfaces. Explicit integration over cyclic variables reduces the sign problem for the initial distribution in the general case. A new application for the simulation of vibronic spectra is described and promising results are presented for a model system. (C) 2016 Elsevier B.V. All rights reserved.
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