离子-分子H+(H2O)n (n = 2-6)配合物的结构及气体气氛中质子水化的热力学特性

IF 1 4区 物理与天体物理 Q3 PHYSICS, MULTIDISCIPLINARY
V. V. Reshetnyak, O. B. Reshetnyak, A. V. Filippov
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引用次数: 0

摘要

用量子化学方法研究了离子分子H+(H2O)n络合物的同分异构体,包括多达6个水分子。用跳盆算法计算了同分异构体中对应于全局最小值和最深局部最小值的原子位置。估计了一些构型变换的活化能。在谐波近似下确定了配合物聚类和分解的热力学特性,与实验数据吻合较好。通过对能量接近的同分异构体的各种通道的热力学特性求平均值,可以简化反应的理论研究。反应的熵对配合物的大小有微弱的依赖性。提出了一个简化模型来解释计算结果,并将其用于估计复杂聚类和分解反应的熵,与实验结果吻合较好。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Structure of Ion–Molecular H+(H2O)n (n = 2–6) Complexes and the Thermodynamic Characteristics of Proton Hydration in Gas Atmosphere

Structure of Ion–Molecular H+(H2O)n (n = 2–6) Complexes and the Thermodynamic Characteristics of Proton Hydration in Gas Atmosphere

The isomers of ion–molecular H+(H2O)n complexes including up to six water molecules have been studied using quantum chemistry methods. The atomic positions in the isomers corresponding to the global and deepest local minima of potential energy are calculated using the basin-hopping algorithm. The activation energies of some configuration transformations are estimated. The thermodynamic characteristics of the clustering and decomposition of complexes are determined in a harmonic approximation, and they are in good agreement with experimental data. The possibility of simplifying the theoretical investigation of reactions by averaging the thermodynamic characteristics over various channels for energetically close isomers is shown. A weak dependence of the entropy of a reaction on the complex size has been found. A simplified model is proposed to explain the calculation results, and its use for estimating the entropies of complex clustering and decomposition reactions gives good agreement with the experimental results.

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来源期刊
CiteScore
1.90
自引率
9.10%
发文量
130
审稿时长
3-6 weeks
期刊介绍: Journal of Experimental and Theoretical Physics is one of the most influential physics research journals. Originally based on Russia, this international journal now welcomes manuscripts from all countries in the English or Russian language. It publishes original papers on fundamental theoretical and experimental research in all fields of physics: from solids and liquids to elementary particles and astrophysics.
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