Solvent electronic polarization effect on the electronic transitions in solution: Charge polarizable reference interaction site model self-consistent field approach
Solvent electronic polarization effect on the electronic transitions in solution: Charge polarizable reference interaction site model self-consistent field approach
复制标题
溶剂电子极化对溶液中电子跃迁的影响：电荷极化参考相互作用位点模型自洽场方法
DOI：
10.1063/1.479329
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发表时间：
1999
影响因子：
4.4
通讯作者：
S. Kato
中科院分区：
文献类型：
--
作者：
K. Naka;A. Morita;S. Kato
采用参考相互作用位点模型自洽场（RISM-SCF）方法研究了溶剂中电子极化对溶质分子激发能溶剂化变色位移的影响。溶剂分子中的电子极化由从头计算得到的电荷响应核（CRK）表示。利用 CRK，提出了一种电荷极化 RISM-SCF 方法来描述溶液中溶质分子的电子结构并估计激发能。计算了 CH3CN、 CHCl3、 CCl4 和 CS2 溶剂中丙酮 nπ* 跃迁的激发能，并考察了溶剂电子极化对溶剂化位移的影响。结果，在这些溶剂中获得了 1225、675、166 和 92 cm-1 的蓝移。此外，在相同的溶剂中评估了吡啶向 11B1、 11B2 和 21A1 态转变中的溶剂化位移。在所有溶剂中观察到 11B1 ← 11A1 转变出现蓝移，w...
Effect of the electronic polarization in solvent on the solvatochromic shift for the excitation energy of solute molecule is studied by the reference interaction site model self-consistent field (RISM-SCF) method. The electronic polarization in solvent molecule is represented by the charge response kernel (CRK) obtained by ab initio calculations. Employing the CRK, a charge polarizable RISM-SCF method is proposed for describing the electronic structure of solute molecules in solution and estimating the excitation energies. The excitation energy for nπ* transition of acetone is calculated in CH3CN, CHCl3, CCl4, and CS2 solvents and the solvent electronic polarization effect on the solvation shift is examined. As a result, a blue shifts of 1225, 675, 166, and 92 cm−1 is obtained in those solvents. Furthermore, the solvation shifts in the transitions to the 11B1, 11B2, and 21A1 states of pyridine are evaluated in the same solvents. A blue shift is observed for the 11B1 ← 11A1 transition in all the solvent, w...