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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >HCl hydrates as model systems for protonated water
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HCl hydrates as model systems for protonated water

机译：HCl水合物作为质子化水的模型系统

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Ab initio molecular dynamics simulations are presented of vibrational dynamics and spectra of crystal HCl hydrates. Depending on the composition, the hydrates include distinct protonated water forms, which in their equilibrium structures approximate either the Eigen ion H3O+(H2O)(3) (in the hexahydrate) or the Zundel H2O center dot center dot center dot H+center dot center dot center dot OH2 ion (in the di- and trihydrate). Thus, the hydrates offer the opportunity to study spectra and dynamics of distinct species of protonated water trapped in a semirigid solvating environment. The experimentally measured spectra are reproduced quite well by BLYP/DZVP-level calculations employing Fourier transform of the system dipole. The large overall width (800-1000 cm(-1)) of structured proton bands reflects a broad range of solvating environments generated by crystal vibrations. The aqueous HCl solution was also examined in search of an objective criterion for separating the contributions of "Zundel-like" and "Eigen-like" protonated forms. It is suggested that no such criterion exists since distributions of proton-related structural properties appear continuous and unimodal. Dipole derivatives with respect to OH and O center dot center dot center dot H+ stretches in water and protonated water were also investigated to advance the understanding of the corresponding IR intensities. The effects of H bonding and solvation on the intensities were analyzed with the help of the Wannier centers' representation of electron density.
机译：从头开始进行分子动力学模拟，研究了晶体HCl水合物的振动动力学和光谱。根据组成，水合物包括不同的质子化水形式，其平衡结构中的本征离子H3O +（H2O）（3）（在六水合物中）或Zundel H2O中心点中心点中心点中心点H +中心点中心点中心点OH2离子（在二水合物和三水合物中）。因此，水合物提供了研究半刚性溶剂化环境中截留的质子化水不同物种的光谱和动力学的机会。通过使用系统偶极子的傅立叶变换的BLYP / DZVP级计算，可以很好地再现实验测量的光谱。结构化质子带的大整体宽度（800-1000 cm（-1））反映了晶体振动产生的各种溶剂化环境。还检查了HCl水溶液，以寻找用于分离“ Zundel样”和“ Eigen样”质子化形式的贡献的客观标准。建议不存在这样的标准，因为质子相关的结构特性分布呈现连续和单峰态。还研究了有关水和质子化水中OH和O中心点中心点中心点H +拉伸的偶极导数，以增进对相应IR强度的理解。借助Wannier中心表示的电子密度，分析了氢键和溶剂化对强度的影响。

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