An Ab Initio QM/MM-Based Approach to Efficiently Evaluate Vertical Excitation Energies in Condensed Phases Including the Nonequilibrium Solvation Effect.
An efficient quantum mechanical/molecular mechanics-based approach is presented to calculate a vertical excitation energy of a chromophore in condensed phases including the nonequilibrium solvation effect. The electronic polarization of a medium and the related nonequilibrium solvation effect associated with the vertical excitation are described using a polarizable solvent model. By virtue of the mean-field approximation, the target energy can be completely separated into classical and quantum mechanical parts, which enables us to efficiently evaluate the vertical excitation energy with a high-level quantum mechanical method. The method is applied to N,N-dimethyl-4-nitroaniline in a variety of solutions at the MRMP2/CASSCF level, showing quantitative agreement with the experimental reports. The observed large bathochromic shifts are analyzed by focusing on the induction effects of the solvents.
Department of Molecular Engineering, Kyoto University , Kyoto 615-8510, Japan.|Elements Strategy Initiative for Catalysts and Batteries, Kyoto University , Kyoto 615-8510, Japan.
Hiroshi
H
Nakano
Department of Molecular Engineering, Kyoto University , Kyoto 615-8510, Japan.|Elements Strategy Initiative for Catalysts and Batteries, Kyoto University , Kyoto 615-8510, Japan.
Hirofumi
H
Sato