Hydrogen bonding in the gas phase: the infrared spectra of complexes of hydrogen fluoride with hydrogen cyanide and methyl cyanide
Hydrogen bonding in the gas phase: the infrared spectra of complexes of hydrogen fluoride with hydrogen cyanide and methyl cyanide
复制标题
气相氢键：氟化氢与氰化氢和甲基氰络合物的红外光谱
DOI：
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发表时间：
1971
期刊：
影响因子：
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通讯作者：
R. Thomas
中科院分区：
文献类型：
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作者：
R. Thomas
在 200 至 4000 cm-1 范围内测量了气相配合物 HCN-HF、DCN-DF 和 CH3CN-HF 四种同位素的红外光谱。观察到两条带，一条与配合物中 HF 的伸缩振动相关，另一条与氢键本身的弯曲振动相关。在更高分辨率下，两个能带都显示出精细结构，这已被解释为与氢键的另一个低频弯曲振动的激发能级的跃迁相关的一系列热能带。在第一个能带中，峰值是各个热能带中的 P 分支带头，在第二个能带中，它们是尖锐的 Q 分支。根据这些带的温度研究以及同位素替代对精细结构间距的影响，已经确定了较低弯曲振动的频率。第一能带中的进一步结构给出了氢键本身的伸缩振动的频率。因此，与氢键相关的所有振动都已完成。根据两个弯曲运动的频率（对于 HCN-HF 复合物为 555 和 70 cm-1），计算了弯曲力常数值。还测量了几个非谐常数，并讨论了非谐性对与氢键相关的能带宽度的影响。
The infrared spectra of the gas phase complexes HCN-HF, DCN-DF and four isotopic species of CH3CN-HF have been measured over the range 200 to 4000 cm-1. Two bands have been observed, one associated with the stretching vibration of HF in the complex and the other with a bending vibration of the hydrogen bond itself. At higher resolution both bands show fine structure which has been interpreted as being a series of hot bands associated with transitions from excited levels of another low-frequency bending vibration of the hydrogen bond. In the first band the peaks are P branch bandheads in the individual hot bands and in the second band they are sharp Q branches. From temperature studies of these bands and from the effects of isotopic substitution on the spacing of the fine structure the frequency of the lower bending vibration has been determined. Further structure in the first band gives the frequency of the stretching vibration of the hydrogen bond itself. A complete assignment of all the vibrations associated with the hydrogen bond has therefore been made. From the frequencies of the two bending motions (555 and 70 cm-1 for the HCN-HF complex) values of the bending force constants have been calculated. Several anharmonic constants have also been measured and the effect of anharmonicity on the breadth of bands associated with the hydrogen bond is discussed.