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首页> 外文期刊>The Journal of Chemical Physics >A wave-function based approach for polarizable charge model: Systematiccomparison of polarization effects on protic, aprotic, and ionic liquids
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A wave-function based approach for polarizable charge model: Systematiccomparison of polarization effects on protic, aprotic, and ionic liquids

机译：可极化电荷模型的基于波函数的方法：质子，非质子和离子液体极化效应的系统比较

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摘要

We first describe a wave-function based formalism of polarizable charge model by starting from theHartree product ansatz for the total wave function and making the second-order expansion ofindividual molecular energies with the use of partial charge operators. The resulting model is shownto be formally equivalent to the charge response kernel model that starts from the linear-responseapproximation to partial charges, and also closely related to a family of fluctuating charge modelsthat are based on the electronegativity equalization principle. We then apply the above model to asystematic comparison of polarization effects on qualitatively different liquids, namely, proticsolvents (water and methanol), an aprotic polar solvent (acetonitrile), and imidazolium-based ionicliquids. Electronic polarization is known to decelerate molecular motions in conventional solventswhile it accelerates them in ionic liquids. To obtain more insights into these phenomena, weconsider an effective decomposition of total polarization energy into molecular contributions, andshow that their statistical distribution is well-correlated with the acceleration/deceleration ofmolecular motions. In addition, we perform effective nonpolarizable simulations based on meanpolarized charges, and compare them with fully polarizable simulations. The result shows that theformer can reproduce structural properties of conventional solvents rather accurately, while they failqualitatively to reproduce acceleration of molecular motions in ionic liquids.
机译：我们首先通过从Hartree乘积ansatz开始计算总波函数，并使用部分电荷算子对单个分子能量进行二阶展开，来描述基于波函数的可极化电荷模型的形式主义。所显示的模型在形式上等效于从线性响应近似到部分电荷的电荷响应核模型，并且还与基于电负性均衡原理的一系列波动电荷模型密切相关。然后，我们将上述模型用于对质子不同的液体（质子溶剂（水和甲醇），非质子极性溶剂（乙腈）和咪唑基离子液体）的极化效应进行系统比较。已知电子极化会降低常规溶剂中的分子运动，同时又会加速离子液体中的分子运动。为了获得对这些现象的更多了解，我们考虑了将总极化能有效分解为分子贡献的方法，并表明它们的统计分布与分子运动的加速/减速密切相关。此外，我们基于平均极化电荷执行有效的不可极化仿真，并将其与完全极化仿真进行比较。结果表明，前者可以相当准确地再现常规溶剂的结构特性，而定性地不能再现离子液体中分子运动的加速。

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