Effective Two-Body Interactions
Effective Two-Body Interactions
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DOI：
10.1021/acs.jpca.1c05677
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发表时间：
2021-08-30
影响因子：
2.9
通讯作者：
Head-Gordon, Martin
中科院分区：
文献类型：
--
作者：
Mackie, Cameron;Zech, Alexander;Head-Gordon, Martin
协同或非相加效应有助于簇或凝聚相中两个分子的成对非共价相互作用，其方式取决于构成其环境的其他周围分子的特定排列和相互作用。给出了有效的二体相互作用的一般表达式，它对多体展开中的升阶是正确的。最简单的结果，通过三阶修正，只需要七个单独的计算，而不是线性的三体贡献。给出了两个应用实例。首先，对完成中心水-水氢键第一溶剂化壳层的模型(H2O)(8)进行了误差分析。能量分解分析表明，协同效应对中心氢键的最大影响来自于电极化。其次，刻画了HCl+(H2O)(4)团簇中质子转移的协同效应的性质。
Cooperative or nonadditive effects contribute to the pairwise noncovalent interaction of two molecules in a cluster or the condensed phase in ways that depend on the specific arrangements and interactions of the other surrounding molecules that constitute their environment. General expressions for an effective two-body interaction are presented, which are correct to increasing orders in the many-body expansion. The simplest result, correct through third order, requires only seven individual calculations, in contrast to a linear number of three-body contributions. Two applications are presented. First, an error analysis is performed on a model (H2O)(8) cluster which completes the first solvation shell of a central water-water hydrogen bond. Energy decomposition analysis is performed to show that the largest effects of cooperativity on the central hydrogen bond arise from electrical polarization. Second, the nature of cooperative effects on proton transfer in an HCl + (H2O)(4) cluster is characterized.