On the applicability of centroid and ring polymer path integral molecular dynamics for vibrational spectroscopy

被引:199
作者
Witt, Alexander [1 ]
Ivanov, Sergei D. [1 ]
Shiga, Motoyuki [1 ]
Forbert, Harald [1 ]
Marx, Dominik [1 ]
机构
[1] Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany
关键词
infrared spectra; molecular dynamics method; vibrational states; QUANTUM-STATISTICAL MECHANICS; TIME-CORRELATION-FUNCTIONS; CANONICAL ENSEMBLE; INFRARED-SPECTRUM; HYDROGEN; FORMULATION; SIMULATION; DENSITY; ALGORITHMS; DIFFUSION;
D O I
10.1063/1.3125009
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
Centroid molecular dynamics (CMD) and ring polymer molecular dynamics (RPMD) are two conceptually distinct extensions of path integral molecular dynamics that are able to generate approximate quantum dynamics of complex molecular systems. Both methods can be used to compute quasiclassical time correlation functions which have direct application in molecular spectroscopy; in particular, to infrared spectroscopy via dipole autocorrelation functions. The performance of both methods for computing vibrational spectra of several simple but representative molecular model systems is investigated systematically as a function of temperature and isotopic substitution. In this context both CMD and RPMD feature intrinsic problems which are quantified and investigated in detail. Based on the obtained results guidelines for using CMD and RPMD to compute infrared spectra of molecular systems are provided.
引用
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页数:15
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