Walsh MS, Xu LH, Lees RM, Mukhopadhyay I, Moruzzi G, Winnewisser BP, Albert S, Butler RA, DeLucia FC
Department of Physics, University of New Brunswick, Fredericton, New Brunswick, E3B 5A3, Canada
J Mol Spectrosc. 2000 Nov;204(1):60-71. doi: 10.1006/jmsp.2000.8201.
New millimeter-wave and microwave measurements for CH(3)OD have been combined with previous literature data and with an extended body of Fourier transform far-infrared observations in a full global analysis of the first two torsional states (v(t) = 0 and 1) of the ground vibrational state. The fitted CH(3)OD data set contained 564 microwave and millimeter-wave lines and 4664 far-infrared lines, representing the most recent available information in the quantum number ranges J </= 20 and K </= 15. A 53-parameter converged global fit was achieved with an overall weighted standard deviation of 1.060, essentially to within the assigned measurement uncertainties of +/-100 kHz for almost all of the microwave and millimeter-wave lines and +/-6 MHz for the far-infrared lines. The new parameters for CH(3)OD are compared to previous results obtained for the (12)CH(3)OH, (13)CH(3)OH, and CD(3)OH isotopomers over the same quantum number ranges using the identical fitting program. Strong asymmetry-induced coupling between the accidentally near-degenerate 0E and -1E v(t) = 0 substates is successfully modeled by the fit. Copyright 2000 Academic Press.
对CH(3)OD进行的新毫米波和微波测量，已与先前文献数据以及大量扩展的傅里叶变换远红外观测数据相结合，用于对基振动态的前两个扭转态（v(t)=0和1）进行全面的全局分析。拟合的CH(3)OD数据集包含564条微波和毫米波谱线以及4664条远红外谱线，代表了量子数范围J≤20和K≤15内最新的可用信息。实现了一个包含53个参数的收敛全局拟合，总体加权标准偏差为1.060，几乎所有微波和毫米波谱线的测量不确定度为±100 kHz，远红外谱线的测量不确定度为±6 MHz，基本都在指定范围内。使用相同的拟合程序，将CH(3)OD的新参数与在相同量子数范围内为(12)CH(3)OH、(13)CH(3)OH和CD(3)OH同位素异构体获得的先前结果进行了比较。拟合成功地模拟了在意外近简并的0E和-1E v(t)=0子态之间强烈的不对称诱导耦合。版权所有2000年学术出版社。
