期刊
JOURNAL OF CHEMICAL PHYSICS
卷 141, 期 15, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4897561
关键词
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资金
- Japan Society for the Promotion of Science (JSPS), Japan
- Strategic Programs for Innovative Research (SPIRE)
- Computational Materials Science Initiative (CMSI)
- MEXT (Ministry of Education Culture, Sports, Science and Technology, Japan) program Elements Strategy Initiative to Form Core Research Center
- Grants-in-Aid for Scientific Research [26410026] Funding Source: KAKEN
Solvent effects on electronic excitation spectra are considerable in many situations; therefore, we propose an efficient and reliable computational scheme that is based on the symmetry-adapted cluster-configuration interaction (SAC-CI) method and the polarizable continuum model (PCM) for describing electronic excitations in solution. The new scheme combines the recently proposed first-order PCM SAC-CI method with the PTE (perturbation theory at the energy level) PCM SAC scheme. This is essentially equivalent to the usual SAC and SAC-CI computations with using the PCM Hartree-Fock orbital and integrals, except for the additional correction terms that represent solute-solvent interactions. The test calculations demonstrate that the present method is a very good approximation of the more costly iterative PCM SAC-CI method for excitation energies of closed-shell molecules in their equilibrium geometry. This method provides very accurate values of electric dipole moments but is insufficient for describing the charge-transfer (CT) indices in polar solvent. The present method accurately reproduces the absorption spectra and their solvatochromism of push-pull type 2,2'-bithiophene molecules. Significant solvent and substituent effects on these molecules are intuitively visualized using the CT indices. The present method is the simplest and theoretically consistent extension of SAC-CI method for including PCM environment, and therefore, it is useful for theoretical and computational spectroscopy. (C) 2014 AIP Publishing LLC.
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