Raman spectroscopic and calculated vibrational wavenumbers of anion hydrates
Raman spectroscopic and calculated vibrational wavenumbers of anion hydrates
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DOI：
10.1002/jrs.844
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发表时间：
2002-03
影响因子：
2.5
通讯作者：
J. D. Craig
中科院分区：
文献类型：
--
作者：
J. D. Craig
检查了氟化物和其他阴离子的阴离子氢键的直接实验证据。分配给对称氢键拉伸模式的偏振拉曼带的中心波数与除氟化物之外的所有阴离子的从头计算非常一致，其理论波数明显高于光谱值。在更高的理论水平上重复计算，但差异仍然存在。氟化物和其他水合物的重水同位素位移和氢键拉伸运动的势能表面相似，表明差异可能是由于与其他分子的相互作用造成的。据推测，氟离子周围的水簇形成导致了波数的差异。版权所有 © 2002 约翰威利父子有限公司
Direct experimental evidence of anion hydrogen bonding was examined for fluoride and other anions. The centre wavenumber of the polarized Raman band assigned to the symmetric hydrogen bond stretching mode agreed very well with ab initio calculations for all anions but fluoride, whose theoretical wavenumber was significantly higher than the spectroscopic value. Calculations were repeated at a higher level of theory but the difference persisted. The heavy water isotope shifts and the potential energy surface for the hydrogen bond stretching motion were similar for fluoride and the other hydrates, suggesting that the difference could be due to interactions with other molecules. It was postulated that water cluster formation about the fluoride ion contributes to the difference in wavenumbers. Copyright © 2002 John Wiley & Sons, Ltd.