Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University , Atlanta, Georgia 30322, United States.
J Am Chem Soc. 2014 Apr 23;136(16):5888-91. doi: 10.1021/ja501986t. Epub 2014 Apr 11.
Coupled intramolecular and intermolecular vibrational quantum dynamics, using an ab initio potential energy surface, successfully describes the subpicosecond relaxation of the OD and OH stretch fundamental and first overtone of dilute HOD in ice Ih. The calculations indicate that more than one intermolecular mode along with the three intramolecular modes is needed to describe the relaxation, in contrast to a recent study using a phenomenological potential in just two degrees of freedom. Detailed time-dependent relaxation pathways from 6-mode calculations are also given.
使用从头算势能面，成功描述了稀 HOD 在冰 Ih 中 OD 和 OH 伸缩基频和第一泛频的亚皮秒弛豫的分子内和分子间耦合振动量子动力学。计算表明，与最近使用唯象势在两个自由度中研究的情况相反，需要多个分子间模式以及三个分子内模式来描述弛豫。还给出了 6 模式计算的详细的时变弛豫途径。
