Solvent effect on vertical electronic transitions by the polarizable continuum model
Solvent effect on vertical electronic transitions by the polarizable continuum model
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DOI：
10.1063/1.480808
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发表时间：
2000-02-01
影响因子：
4.4
通讯作者：
Barone, V
中科院分区：
文献类型：
--
作者：
Cossi, M;Barone, V
将极化连续溶剂化模型(PCM)扩展到激发电子态，研究了溶剂对电子跃迁的影响，考虑了静电和非静电溶质-溶剂相互作用。发展了适用于所有PCM模型的非平衡静电溶剂化的一般形式，并首次实现和使用了最新的色散和排斥溶质-溶剂相互作用的量子力学计算方法。该程序被应用于丙酮在水和非水溶剂中的n-->；pi*转变的研究：在极性环境中，非平衡效应是非常重要的；此外，为了获得溶剂变色位移的正确趋势，必须包括分散和排斥。还分析了添加显性溶剂分子的效果。(C)2000年美国物理研究所。[S0021-9606(00)53205-X]。
A recent extension of the polarizable continuum solvation model (PCM) to excited electronic states is applied to the study of solvent effects on electronic transitions, accounting for both electrostatic and nonelectrostatic solute-solvent interactions. A general formalism for nonequilibrium electrostatic solvation is developed, applicable to all PCM versions, and a recent procedure for the quantum-mechanical computation of dispersion and repulsion solute-solvent interactions is implemented and used for the first time in this context. The procedure is applied to the study of the n -->pi* transition of acetone in aqueous and nonaqueous solvents: nonequilibrium effects are very important in polar environments; also, the inclusion of dispersion and repulsion is mandatory to obtain the correct trend of the solvatochromic shifts. The effect of adding some explicit solvent molecules is also analyzed. (C) 2000 American Institute of Physics. [S0021-9606(00)53205-X].