Second Hyperpolarizability of C-H, C-D, and C N Stretch Vibrations   Determined from Computational Raman Activities and a Comparison with   Experiments

doi:10.1021/jp4073119

CORC > 北京大学 > 化学与分子工程学院

	Second Hyperpolarizability of C-H, C-D, and C N Stretch Vibrations Determined from Computational Raman Activities and a Comparison with Experiments
	Zhao, Wei ; He, Anqi ; Xu, Yizhuang
刊名	journal of physical chemistry b
	2013
关键词	DENSITY-FUNCTIONAL THEORY ENHANCED 4-WAVE-MIXING SPECTROSCOPY RESONANCE RAMAN BASIS-SETS SPECTRA INTENSITIES DFT ASSIGNMENT ACETONITRILE TETRAHYDROFURAN
DOI	10.1021/jp4073119
英文摘要	We have recently demonstrated that the second hyperpolarizability gamma of a selected vibrational mode of a molecule can be determined by using the computational Raman activity against an internal standard with a known Raman gamma value. This approach provides a convenient way for prediction of the gamma magnitude of DOVE four wave mixing spectroscopy, an optical analogue to two-dimensional (2D) NMR. Here, by using the Hartree-Fock (HF) method, the density functional theory (DFT) method, and the second-order Moller-Plesset perturbation theory (MP2) method, we extend our early work from the less anharmonic region <2000 cm(-1) into the more anharmonic region >2000 cm(-1) covering C-H, C-D, and C N stretching modes of benzene, deuterated benzene, acetonitrile, deuterated acetonitrile, and tetrahydrofuran. The computed Raman gamma values of these vibrational modes have been determined by using either the 992 cm(-1) Raman band of benzene or the compound's own Raman band (C-C stretch) around 800-1000 cm(-1) as an internal standard. In this more anharmonic region, the HF method with a larger basis set provides the best outputs and the predicted Raman gamma values agree well with experimental values for most of the vibrational modes studied. By choosing a suitable method and basis set, this facile approach could be applied to a broader spectral range for Raman gamma estimation of various materials.; Chemistry, Physical; SCI(E); EI; 0; ARTICLE; 49,SI; 15812-15818; 117
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/219328]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhao, Wei,He, Anqi,Xu, Yizhuang. Second Hyperpolarizability of C-H, C-D, and C N Stretch Vibrations Determined from Computational Raman Activities and a Comparison with Experiments[J]. journal of physical chemistry b,2013.
APA	Zhao, Wei,He, Anqi,&Xu, Yizhuang.(2013).Second Hyperpolarizability of C-H, C-D, and C N Stretch Vibrations Determined from Computational Raman Activities and a Comparison with Experiments.journal of physical chemistry b.
MLA	Zhao, Wei,et al."Second Hyperpolarizability of C-H, C-D, and C N Stretch Vibrations Determined from Computational Raman Activities and a Comparison with Experiments".journal of physical chemistry b (2013).