An analysis of nonadiabatic ring-polymer molecular dynamics and its application to vibronic spectra

被引：44

作者：

Richardson, Jeremy O. ^{[1
,2
,3
]}

Meyer, Philipp ^{[1
,2
]}

Pleinert, Marc-Oliver ^{[1
,2
]}

Thoss, Michael ^{[1
,2
]}

机构：

[1] Friedrich Alexander Univ Erlangen Nurnberg FAU, Inst Theoret Phys, Staudtstr 7-B2, D-91058 Erlangen, Germany

[2] Friedrich Alexander Univ Erlangen Nurnberg FAU, Interdisziplinares Zentrum Mol Mat, Staudtstr 7-B2, D-91058 Erlangen, Germany

[3] Univ Durham, Dept Chem, South Rd, Durham DH1 3LE, England

来源：

CHEMICAL PHYSICS | 2017年 / 482卷

关键词：

Vibronic spectra; Ring-polymer molecular dynamics; Nonadiabatic; Mapping approach; INITIAL-VALUE REPRESENTATION; MAPPING HAMILTONIAN APPROACH; SEMICLASSICAL DESCRIPTION; ABSORPTION-SPECTRA; PHASE; IMPLEMENTATION; MECHANICS; FREEDOM;

D O I：

10.1016/j.chemphys.2016.09.036

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：124 / 134

页数：11