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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Influence of structure on electron correlation effects and electron-water dispersion interactions in anionic water clusters
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Influence of structure on electron correlation effects and electron-water dispersion interactions in anionic water clusters

机译：结构对阴离子水团簇中电子相关效应和电子水分散相互作用的影响

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Electronic structure calculations at the level of second-order Moller-Plesset perturbation theory have been performed on anionic water clusters, (H2O)n(-), in the n = 14-33 size regime. The contribution to the electron binding energy that arises from electron correlation is found to be significantly larger for cavity-bound electrons than it is for surface-bound electrons, even for surface states with electron binding energies well above 1 eV. A decomposition of the correlation energy into interactions between pairs of Boys-localized molecular orbitals is used to demonstrate that the larger correlation energy found in the cavity isomers arises from electron-water dispersion interactions, and that the dispersion interaction is larger in cavity-bound isomers because the impaired electron penetrates well beyond the first solvation shell. In contrast, a surface-bound electron exhibits virtually no penetration into the interior of the cavity. To obtain a qualitatively accurate picture of this phenomenon, one must plot molecular orbitals using isoprobability surfaces rather than arbitrarily-selected isocontours.
机译：在n = 14-33尺寸范围内，对阴离子水簇（H2O）n（-）进行了二阶Moller-Plesset微扰理论水平的电子结构计算。已发现，与空穴结合的电子相比，由电子相关性引起的对电子结合能的贡献明显大于对表面结合的电子的贡献，即使对于电子结合能远高于1 eV的表面态也是如此。通过将相关能分解为成对的Boys局部分子轨道之间的相互作用，可以证明在腔型异构体中发现的更大的相关能来自电子-水分散相互作用，并且在型腔结合的异构体中，分散相互作用更大因为受损的电子会远远超出第一个溶剂化壳层。相反，表面结合的电子实际上没有渗透到空腔内部。为了获得对该现象的定性准确描述，必须使用等渗性表面而不是任意选择的等高线绘制分子轨道。

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