Esser Tim K, Knorke Harald, Asmis Knut R, Schöllkopf Wieland, Yu Qi, Qu Chen, Bowman Joel M, Kaledin Martina
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig , Linnéstraße 2, 04103 Leipzig, Germany.
Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, D-14195 Berlin, Germany.
J Phys Chem Lett. 2018 Feb 15;9(4):798-803. doi: 10.1021/acs.jpclett.7b03395. Epub 2018 Feb 5.
We report experimental vibrational action spectra (210-2200 cm) and calculated IR spectra, using recent ab initio potential energy and dipole moment surfaces, of HO and HO. We focus on prominent far-IR bands, which postharmonic analyses show, arise from two types of intermolecular motions, i.e., hydrogen bond stretching and terminal water wagging modes, that are similar in both clusters. The good agreement between experiment and theory further validates the accuracy of the potential and dipole moment surfaces, which was used in a recent theoretical study that concluded that infrared photodissociation spectra of the cold clusters correspond to the Eigen isomer. The comparison between theory and experiment adds further confirmation of the need of postharmonic analysis for these clusters.
我们报告了使用最新的从头算势能和偶极矩面得到的HO和HO的实验振动作用光谱（210 - 2200厘米）以及计算得到的红外光谱。我们关注突出的远红外波段，后谐波分析表明，这些波段源于两种分子间运动，即氢键拉伸和末端水分子摆动模式，这两种模式在两个团簇中相似。实验与理论之间的良好一致性进一步验证了势能和偶极矩面的准确性，在最近的一项理论研究中使用了该准确性，该研究得出结论，冷团簇的红外光解离光谱对应于本征异构体。理论与实验之间的比较进一步证实了对这些团簇进行后谐波分析的必要性。
