Theoretical investigation of the direct observation of anharmonic coupling in CDCl3 in the time domain with femtosecond stimulated Raman scattering

	Theoretical investigation of the direct observation of anharmonic coupling in CDCl3 in the time domain with femtosecond stimulated Raman scattering
	Sun, Zhigang 1,2; Fu, Bina 3,4; Zhang, Dong H.3,4; Lee, Soo-Y.1,2
刊名	journal of chemical physics
	2009-01-28
卷号	130 期号:4 页码:044312-044312
关键词	ab initio calculations ground states molecular configurations molecular moments molecule-photon collisions optical pumping organic compounds potential energy surfaces stimulated Raman scattering transition moments vibrational states
通讯作者	李仕仁
产权排序	2;1
英文摘要	the femtosecond stimulated raman scattering (fsrs) difference spectra of cdcl3 from the ground potential energy surface, with and without off-resonance impulsive stimulated raman pumping, taken at various delay times from the impulsive pump by kukura [phys. rev. lett. 96, 238303 (2006)], showed sidebands of the c-cl bends with periodic changes in phase as well as having an inversion symmetry to the high and low frequency sides of the stokes c-d stretch at 2255 cm(-1). the semiclassical coupled-wave approach and a one-dimensional (1d) oscillator model for the c-d stretch whose frequency is modulated in time by the c-cl bends could account for some features of the experimental results. here, a quantum mechanical investigation is made of the fsrs difference spectra with a modulated 1d oscillator and three-dimensional (3d) harmonic and anharmonic potentials. it is shown that (i) the sidebands are allowed, with or without anharmonic coupling between the c-d stretch and the c-cl bends, (ii) in the 3d harmonic model the sidebands have mirror symmetry about the stokes c-d stretch, (iii) in the 3d anharmonic model with appropriate coupling terms between the c-d stretch and the c-cl bends, the experimental results are well accounted for in both the phase changes in the fsrs difference spectra with time delay as well as the inversion symmetry of the sidebands for the c-cl bends about the stokes c-d stretch, (iv) there is a correspondence between the phase changes in the fsrs difference spectra and the wavepacket motion induced by the impulsive pump pulse on the ground potential energy surface as a function of the delay time, and (v) changing the polarization of the impulsive pump pulse, say, directly affects the coordinate dependence of the linear transition dipole moment in the asymmetric mode and hence its phase in the fsrs difference spectra, but not so for the symmetric modes where the displacement of the excited state surface governs the fsrs difference spectra more than the transition dipole moment. this work illustrates the potential of off-resonance fsrs in studying polyatomic molecular dynamics.
WOS标题词	science & technology ; physical sciences
类目[WOS]	physics, atomic, molecular & chemical
研究领域[WOS]	physics
关键词[WOS]	dynamic absorption-spectra ; pump-probe spectroscopy ; vibrational spectroscopy ; molecular-dynamics
收录类别	SCI
原文出处	false
语种	英语
WOS记录号	WOS:000262965000023
公开日期	2010-11-30
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/101605]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 637371, Singapore 2.Nanyang Technol Univ, Sch Phys & Math Sci, Div Phys & Appl Phys, Singapore 637371, Singapore 3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 4.Chinese Acad Sci, Dalian Inst Chem Phys, Ctr Theoret & Computat Chem, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Sun, Zhigang,Fu, Bina,Zhang, Dong H.,et al. Theoretical investigation of the direct observation of anharmonic coupling in CDCl3 in the time domain with femtosecond stimulated Raman scattering[J]. journal of chemical physics,2009,130(4):044312-044312.
APA	Sun, Zhigang,Fu, Bina,Zhang, Dong H.,&Lee, Soo-Y..(2009).Theoretical investigation of the direct observation of anharmonic coupling in CDCl3 in the time domain with femtosecond stimulated Raman scattering.journal of chemical physics,130(4),044312-044312.
MLA	Sun, Zhigang,et al."Theoretical investigation of the direct observation of anharmonic coupling in CDCl3 in the time domain with femtosecond stimulated Raman scattering".journal of chemical physics 130.4(2009):044312-044312.