Computing Wigner distributions and time correlation functions using the quantum thermal bath method: application to proton transfer spectroscopy

被引:33
作者
Basire, Marie [1 ]
Borgis, Daniel [1 ]
Vuilleumier, Rodolphe [1 ]
机构
[1] Ecole Normale Super, Theoret Phys Chem Grp, Dept Chim, UMR CNRS ENS UPMC 8640, F-75005 Paris, France
关键词
INITIAL-VALUE REPRESENTATION; ADIABATIC DYNAMIC SIMULATION; H-BONDED COMPLEXES; MOLECULAR-DYNAMICS; VIBRATIONAL-RELAXATION; STATISTICAL MECHANICS; HYDROGEN-BOND; SYSTEMS; FORMULATION; TRANSPORT;
D O I
10.1039/c3cp50493j
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
Langevin dynamics coupled to a quantum thermal bath (QTB) allows for the inclusion of vibrational quantum effects in molecular dynamics simulations at virtually no additional computer cost. We investigate here the ability of the QTB method to reproduce the quantum Wigner distribution of a variety of model potentials, designed to assess the performances and limits of the method. We further compute the infrared spectrum of a multidimensional model of proton transfer in the gas phase and in solution, using classical trajectories sampled initially from the Wigner distribution. It is shown that for this type of system involving large anharmonicities and strong nonlinear coupling to the environment, the quantum thermal bath is able to sample the Wigner distribution satisfactorily and to account for both zero point energy and tunneling effects. It leads to quantum time correlation functions having the correct short-time behavior, and the correct associated spectral frequencies, but that are slightly too overdamped. This is attributed to the classical propagation approximation rather than the generation of the quantized initial conditions themselves.
引用
收藏
页码:12591 / 12601
页数:11
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