کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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5372785 | 1504186 | 2017 | 11 صفحه PDF | دانلود رایگان |
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.
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Journal: Chemical Physics - Volume 482, 12 January 2017, Pages 124-134