ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxon, United Kingdom.
J Chem Phys. 2011 Feb 28;134(8):084503. doi: 10.1063/1.3553812.
The assignment of the vibrational spectra of lithium hydroxide monohydrate, LiOH·H(2)O, has been controversial for more than half-a-century. Here we show that only the combination of all three forms of vibrational spectroscopy: infrared, Raman and inelastic neutron scattering spectroscopies coupled with periodic-density functional theory calculations is able to satisfactorily assign the spectra. All previous work based on empirical criteria is, at least partially, incorrect. The librational modes of water do not follow the expected rock > wag > twist order and the calculations indicate that complete or partial deuterium substitution would not be useful in assigning the modes.
一水合氢氧化锂（LiOH·H2O）的振动光谱的分配问题已经争论了半个多世纪。在这里，我们表明，只有将三种形式的振动光谱：红外、拉曼和非弹性中子散射光谱与周期性密度泛函理论计算相结合，才能令人满意地对光谱进行分配。以前所有基于经验标准的工作至少在某些方面是不正确的。水的摆动模式不遵循预期的“rock > wag > twist”顺序，并且计算表明，完全或部分氘取代在分配模式时不会有用。
