A semiclassical initial-value representation for quantum propagator and boltzmann operator

被引:2
|
作者
Yan, Yun-An [1 ]
Liu, Jian [2 ]
Shao, Jiushu [3 ,4 ]
机构
[1] Ludong Univ, Sch Phys & Optoelect Engn, Yantai 264025, Shandong, Peoples R China
[2] Peking Univ, Coll Chem & Mol Engn, Inst Theoret & Computat Chem, Beijing Natl Lab Mol Sci, Beijing 100871, Peoples R China
[3] Beijing Normal Univ, Minist Educ, Coll Chem, Beijing 100875, Peoples R China
[4] Beijing Normal Univ, Minist Educ, Ctr Adv Quantum Studies, Key Lab Theoret & Computat Photochem, Beijing 100875, Peoples R China
基金
中国国家自然科学基金;
关键词
correction operator; Boltzmann operator; imaginary-time semiclassical approximation; semiclassical dynamics; PATH-INTEGRALS; PHASE-SPACE; STATISTICAL-MECHANICS; TIME EVOLUTION; S-MATRIX; APPROXIMATIONS; DERIVATION; SYSTEMS;
D O I
10.1002/jcc.25751
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Starting from the position-momentum integral representation, we apply the correction operator method to the derivation of a uniform semiclassical approximation for the quantum propagator and then extend it to approximate the Boltzmann operator. In this approach, the involved classical dynamics is determined by the method itself instead of given beforehand. For the approximate Boltzmann operator, the corresponding classical dynamics is governed by a complex Hamiltonian, which can be described as a pair of real Hamiltonian systems. It is demonstrated that the semiclassical Boltzmann operator is exact for linear systems. A quantum propagator in the complex time is thus proposed and preliminary numerical results show that it is a reasonable approximation for calculating thermal correlation functions of general systems. (c) 2018 Wiley Periodicals, Inc.
引用
收藏
页码:1161 / 1171
页数:11
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