The Graduate University for Advanced Studies, Myodaiji, Okazaki, Aichi 444-8585, Japan.
J Chem Phys. 2013 Jul 28;139(4):044503. doi: 10.1063/1.4813071.
Frequency fluctuations of the OH stretch and the HOH bend in liquid water are reported from the third-order response function evaluated using the TTM3-F potential for water. The simulated two-dimensional infrared spectra of the OH stretch are similar to previously reported theoretical results. The present study suggests that the frequency fluctuation of the HOH bend is faster than that of the OH stretch. The ultrafast loss of the frequency correlation of the HOH bend is due to the strong couplings with the OH stretch as well as the intermolecular hydrogen bond bend.
本文报道了使用 TTM3-F 水势计算得到的三阶响应函数计算得到的液态水中 OH 伸缩和 HOH 弯曲的频率波动。模拟的 OH 伸缩二维红外光谱与之前报道的理论结果相似。本研究表明，HOH 弯曲的频率波动比 OH 伸缩快。HOH 弯曲的频率相关的超快损耗是由于与 OH 伸缩以及分子间氢键弯曲的强耦合。
