Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models
Electronic excitation energies of molecules in solution: State specific and linear response methods for nonequilibrium continuum solvation models
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DOI：
10.1063/1.1867373
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发表时间：
2005-03-08
影响因子：
4.4
通讯作者：
Tomasi, J
中科院分区：
文献类型：
--
作者：
Cammi, R;Corni, S;Tomasi, J
我们提出了一个正式的比较两种不同的方法来计算电子激发能的分子在溶液中的连续溶剂化模型框架内，也考虑到非平衡效应。这两种方法，一种是基于显式评价的激发态波函数的溶质和其他的线性响应理论的基础上，在这里被证明给正式不同的表达式的激发能量，即使当被认为是确切的本征态。对一些说明性实例进行的计算表明，这种形式差异对绝对溶剂化变色位移具有明显的影响（即，相对于气相）而对相对（即，非极性到极性溶剂）溶剂化变色位移。
We present a formal comparison between the two different approaches to the calculation of electronic excitation energies of molecules in solution within the continuum solvation model framework, taking also into account nonequilibrium effects. These two approaches, one based on the explicit evaluation of the excited state wave function of the solute and the other based on the linear response theory, are here proven to give formally different expressions for the excitation energies even when exact eigenstates are considered. Calculations performed for some illustrative examples show that this formal difference has sensible effects on absolute solvatochromic shifts (i.e., with respect to gas phase) while it has small effects on relative (i.e., nonpolar to polar solvent) solvatochromic shifts.