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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structural Isomerism and Competitive Proton Solvation between Methanol and Water in H~+(CH_3OH)m(H_2O)n, m + n = 4
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Structural Isomerism and Competitive Proton Solvation between Methanol and Water in H~+(CH_3OH)m(H_2O)n, m + n = 4

机译：H〜+（CH_3OH）m（H_2O）n，m + n = 4中甲醇与水的结构异构和竞争性质子溶剂化

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摘要

Competitive solvation of the excess proton in protonated mixed methanol-water clusters [H~+(CH_3OH)m(H_2O)_n, m + n = 4] has been characterized by vibrational predissociation spectroscopy in combination with density functional theory calculations. The solvation topology of the clusters can be classified as (1) the closed shell, in which a hydronium ion H_3O~+ is fully solvated by three neutral molecules forming a complete solvation shell, and (2) the open chain, where the excess proton is tugged between two mixed subunits in a linear chain. The existence of these two types of isomer is verified from a close examination of the characteristic free-OH and hydrogen-bonded-OH stretching modes in the spectra. It is found that sequential replacement of the water molecule in H~+(H_2O)_4 by methanol redistributes the population between the closed-shell and the open-chain isomers. While the excess proton is preferentially taken by methanol (instead of water) in the chain configuration, it can be either localized as CH_3OH_2~+ or delocalized as CH_3OH···H~+···CH_3OH at m ≥ 2, depending sensitively on the number of the methanol molecules and the symmetry of the cluster isomers. In contrast to that of NH_4~+(NH_3)m(H_2O)n, m + n = 4, previously studied, this work provides a clear picture of competitive solvation of a charge between the constituent solvent molecules within a cluster.
机译：质子化的混合甲醇-水簇[H〜+（CH_3OH）m（H_2O）_n，m + n = 4]中质子的竞争溶剂化已通过振动预离解光谱结合密度泛函理论计算来表征。团簇的溶剂化拓扑可分类为（1）封闭壳，其中氢离子H_3O〜+被三个中性分子完全溶剂化形成一个完整的溶剂化壳，和（2）开放链，其中过量的质子在线性链的两个混合亚基之间被拉。通过仔细检查光谱中特征性的游离OH和氢键合OH拉伸模式，可以验证这两种类型异构体的存在。发现用甲醇顺序替换H〜+（H_2O）_4中的水分子可在闭壳和开链异构体之间重新分配种群。虽然过量的质子优先以甲醇（而非水）的链状构型吸收，但它可以在m≥2时局域化为CH_3OH_2〜+或局域化为CH_3OH···H〜+···CH_3OH，具体取决于甲醇分子的数目和簇异构体的对称性。与先前研究的NH_4〜+（NH_3）m（H_2O）n，m + n = 4相比，这项工作清楚地说明了簇中组成溶剂分子之间的电荷竞争性溶剂化。

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