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低温下的腔衰荡和傅里叶变换红外光谱(84-297 K):CHD(3)的 C-H 基频和泛频(Delta(upsilon) = 1-6)跃迁的费米共振和强度。

Cavity ring down and Fourier transform infrared spectroscopy at low temperatures (84-297 K): Fermi resonance and intensities of the C-H fundamental and overtone (Delta(upsilon) = 1-6) transitions of CHD(3).

机构信息

Department of Chemistry & Biochemistry, Baylor University, 101 Bagby Avenue, Baylor Sciences Building E-216, Waco, Texas 76706, USA.

出版信息

J Phys Chem A. 2010 Aug 5;114(30):7918-27. doi: 10.1021/jp105382p.

Abstract

The C-H stretch fundamental and overtone absorptions of CHD(3) have been obtained using Fourier transform infrared (FTIR), near-infrared, and phase shift and pulsed cavity ring down (CRD) techniques at temperatures between 84 and 297 K. The partially resolved rotational-vibrational spectra of CHD(3) that included the fundamental transition nu(1), the overtone transitions, and combination bands 5nu(1) and 4nu(1) + 2nu(5) and 6nu(1) and 5nu(1) + 2nu(5) were obtained and compared with the simulated spectra at the corresponding temperature. The strength of the Fermi resonance between levels upsilonnu(1) and (upsilon - 1)nu(1) + 2nu(5) with upsilon = 2-6 was calculated using the experimental perturbed energies and relative peak intensities. The integrated absorption was calculated as a function of the density of the gas samples and used to obtain the cross section and the band strength of the Deltaupsilon = 5 and 6 transitions. Ab initio molecular orbital calculations were done to obtain the dipole moment function (DMF) as a function of the C-H internuclear distance. Intensity calculations with the DMF correctly predict the order of magnitude of the experimental band strengths.

摘要

采用傅里叶变换红外(FTIR)、近红外和相移以及脉冲腔衰荡(CRD)技术,在 84 至 297 K 的温度范围内,获得了 CHD(3)的 C-H 伸缩基频和泛频吸收。获得了部分分辨的 CHD(3)的转动-振动光谱,其中包括基频跃迁 nu(1)、泛频跃迁以及组合带 5nu(1)和 4nu(1) + 2nu(5)和 6nu(1)和 5nu(1) + 2nu(5),并与相应温度下的模拟光谱进行了比较。利用实验扰动能量和相对峰强度,计算了能级 upsilonnu(1)和 (upsilon - 1)nu(1) + 2nu(5)之间的费米共振强度,其中 upsilon = 2-6。将积分吸收作为气体样品密度的函数进行计算,并用于获得 Deltaupsilon = 5 和 6 跃迁的截面和带强度。进行了从头算分子轨道计算,以获得作为 C-H 核间距离函数的偶极矩函数(DMF)。使用 DMF 进行的强度计算正确地预测了实验带强度的数量级。

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