A frequency-resolved cavity model (FRCM) for treating equilibrium and non-equilibrium solvation energies
A frequency-resolved cavity model (FRCM) for treating equilibrium and non-equilibrium solvation energies
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DOI：
10.1016/s0301-0104(98)00101-3
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发表时间：
1998-06-15
期刊：
影响因子：
2.3
通讯作者：
Newton, MD
中科院分区：
文献类型：
--
作者：
Basilevsky, MV;Rostov, IV;Newton, MD
考虑了一种描述带电溶质在极性溶剂中的溶剂化效应的精细连续介质模型，称为频率分辨空腔模型(FRCM)。普遍接受的Born-Kirkwood-Onsager模型和FRCM处理的主要区别在于，在FRCM处理中，由溶质电荷分布引起的介质极化场被细分为与不同空穴相关的惯性分量和无惯性分量。由溶剂电子极化模产生的无惯性场包括一个限制在较大腔内的内腔，它建立了与溶剂分子在两个腔外的集体定向和平移运动相对应的惯性极化模的边界。该模型适用于复杂的化学溶质，对其空穴形状和电荷分布没有对称性限制。在引入两个空腔时，我们发现在精化模型中选择一个额外的参数来控制不同的空腔大小，能够为FRCM参数化方案提供必要的额外灵活性。通过这种方法，我们可以重新分配对平衡溶剂化能的惯性和无惯性贡献，这种方式与现有的平衡溶剂化能和溶剂重组能的实验数据一致。(C)1998 Elsevier Science B.V.保留所有权利。
A refined continuum medium model, denoted as the 'frequency-resolved cavity model' (FRCM), for describing solvation effects of electrically charged solutes in polar solvents is considered. The principal distinction between the commonly accepted Born-Kirkwood-Onsager model and the FRCM treatment is that in the latter case the medium polarization field induced by the solute charge distribution is subdivided into inertial and inertialess components associated with different cavities. The inertialess field, arising from solvent electronic polarization modes, involves an inner cavity confined inside a larger one, which establishes the boundary for inertial polarization modes corresponding to collective orientational and translational motions of solvent molecules outside both cavities. The model is formulated so as to be applicable to complicated chemical solutes, with no symmetry limitations imposed on the shape of their cavities and charge distributions. In introducing two cavities, we find that a single extra parameter in the refined model, chosen to control the distinct sizes of the cavities, is capable of providing the necessary additional flexibility to the FRCM parametrization scheme. By this means one can redistribute inertial and inertialess contributions to equilibrium solvation energies in a way which is consistent with existing experimental data for both equilibrium solvation energy solvent reorganization energy. (C) 1998 Elsevier Science B.V. All rights reserved.