Local-monomer calculations of the intramolecular IR spectra of the cage and prism isomers of HOD(D2O)5 and HOD and D2O ice Ih.
Local-monomer calculations of the intramolecular IR spectra of the cage and prism isomers of HOD(D2O)5 and HOD and D2O ice Ih.
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DOI：
10.1021/jp5061182
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发表时间：
2014-07
期刊：
影响因子：
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通讯作者：
Hanchao Liu;Yimin Wang;J. Bowman
中科院分区：
文献类型：
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作者：
Hanchao Liu;Yimin Wang;J. Bowman
实验者已经使用HOD在纯H2O和D2 O冰和液体中的稀释混合物来集中于HOD在这些复杂和高度非均匀环境中的局部OH和OD拉伸和弯曲的光谱和振动动力学。该混合物的六聚体形式是HOD（D2 O）5。最近，Skinner及其同事利用红外光谱的局域模计算对该簇的笼状异构体进行了研究和理论分析。这一点和进一步的实验研究的可能性，这个集群刺激我们研究HOD（D2 O）5使用三模式，本地单体模型，从头计算WHBB偶极矩和势能面。笼和棱柱异构体的这个集群被认为是。除了提供对光谱的HOD部分的额外了解之外，每个D2 O的光谱特征也在1000-4000 cm（-1）的范围内呈现。棱柱和笼形同位素异构体的OH伸缩带在3100-3700 cm（-1）范围内显示出丰富的结构，这表明HOD在这些六聚体中的位置。的HOD的网站偏好的初步调查也报告了笼和棱镜HOD（D2 O）5使用谐波零点能量分析的整个集群。这表明自由OH位的能量低于H-键合OH位的能量。最后，根据我们早期对H_2O冰模型的红外光谱的研究，我们给出了纯D_2O和HOD的红外光谱。
Dilute mixtures of HOD in pure H2O and D2O ices and liquid have been used by experimentalists to focus on the spectrum and vibrational dynamics of the local OH and OD stretches and bend of HOD in these complex and highly heterogeneous environments. The hexamer version of the mixture is HOD(D2O)5. The cage isomer of this cluster was recently studied and analyzed theoretically using local-mode calculations of the IR spectrum by Skinner and co-workers. This and the further possibility of experimental investigation of this cluster have stimulated us to study HOD(D2O)5 using the three-mode, local-monomer model, with the ab initio WHBB dipole moment and potential energy surfaces. Both the cage and prism isomers of this cluster are considered. In addition to providing additional insight into the HOD portion of the spectrum, the spectral signatures of each D2O are also presented in the range of 1000-4000 cm(-1). The OH stretch bands of both the prism and cage isotopomers exhibit rich structures in the range of 3100-3700 cm(-1) that are indicative of the position of the HOD in these hexamers. A preliminary investigation of the site preference of the HOD is also reported for both cage and prism HOD(D2O)5 using an harmonic zero-point energy analysis of the entire cluster. This indicates that the energies of free-OH sites are lower than the ones of H-bonded OH sites. Finally, following our earlier work on the IR spectra of H2O ice models, we present IR spectra of pure D2O and HOD.