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题名: Nonperturbative vibrational energy relaxation effects on vibrational line shapes
作者: Yang, SL;  Shao, JS;  Cao, JS
刊名: JOURNAL OF CHEMICAL PHYSICS
发表日期: 2004-12-08
DOI: 10.1063/1.1812748
卷: 121, 期:22, 页:11250-11271
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Physics
英文摘要: A general formulation of nonperturbative quantum dynamics of solutes in a condensed phase is proposed to calculate linear and nonlinear vibrational line shapes. In the weak solute-solvent interaction limit, the temporal absorption profile can be approximately factorized into the population relaxation profile from the off-diagonal coupling and the pure-dephasing profile from the diagonal coupling. The strength of dissipation and the anharmonicity-induced dephasing rate are derived in Appendix A. The vibrational energy relaxation (VER) rate is negligible for slow solvent fluctuations, yet it does not justify the Markovian treatment of off-diagonal contributions to vibrational line shapes. Non-Markovian VER effects are manifested as asymmetric envelops in the temporal absorption profile, or equivalently as side bands in the frequency domain absorption spectrum. The side bands are solvent-induced multiple-photon effects which are absent in the Markovian VER treatment. Exact path integral calculations yield non-Lorentzian central peaks in absorption spectrum resulting from couplings between population relaxations of different vibrational states. These predictions cannot be reproduced by the perturbative or the Markovian approximations. For anharmonic potentials, the absorption spectrum shows asymmetric central peaks and the asymmetry increases with anharmonicity. At large anharmonicities, all the approximation schemes break down and a full nonperturbative path integral calculation that explicitly accounts for the exact VER effects is needed. A numerical analysis of the O-H stretch of HOD in D2O solvent reveals that the non-Markovian VER effects generate a small recurrence of the echo peak shift around 200 fs, which cannot be reproduced with a Markovian VER rate. In general, the nonperturbative and non-Markovian VER contributions have a stronger effect on nonlinear vibrational line shapes than on linear absorption.(C) 2004 American Institute of Physics.
关键词[WOS]: MOLECULAR-DYNAMICS SIMULATIONS ;  QUANTUM-CLASSICAL DYNAMICS ;  BROWNIAN-OSCILLATOR MODEL ;  HYDROGEN-BOND DYNAMICS ;  POPULATION RELAXATION ;  INFRARED-SPECTROSCOPY ;  SEMICLASSICAL THEORY ;  SOLVATION DYNAMICS ;  CONDENSED-PHASE ;  CARBON-MONOXIDE
语种: 英语
WOS记录号: WOS:000225440000048
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/139574
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.MIT, Dept Chem, Cambridge, MA 02139 USA
2.Chinese Acad Sci, State Key Lab Mol React Dynam, Ctr Mol Sci Inst Chem, Beijing 100080, Peoples R China

Recommended Citation:
Yang, SL,Shao, JS,Cao, JS. Nonperturbative vibrational energy relaxation effects on vibrational line shapes[J]. JOURNAL OF CHEMICAL PHYSICS,2004,121(22):11250-11271.
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