TY - JOUR
T1 - Solvent electronic polarization effect on the electronic transitions in solution
T2 - Charge polarizable reference interaction site model self-consistent field approach
AU - Naka, Kazunari
AU - Morita, Akihiro
AU - Kato, Shigeki
PY - 1999/7/8
Y1 - 1999/7/8
N2 - 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 11β1← 11A1 transition in all the solvent, while the 21A1 ← 11A1 one shows a red shift.
AB - 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 11β1← 11A1 transition in all the solvent, while the 21A1 ← 11A1 one shows a red shift.
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U2 - 10.1063/1.479329
DO - 10.1063/1.479329
M3 - Article
AN - SCOPUS:0042725513
VL - 111
SP - 481
EP - 491
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 2
ER -