Symmetry-adapted cluster and symmetry-adapted cluster-configuration interaction method in the polarizable continuum model: Theory of the solvent effect on the electronic excitation of molecules in solution

摘要

In this paper we present the theory and implementation of the symmetry-adapted cluster (SAC) and symmetry-adapted cluster-configuration interaction (SAC-CI) method, including the solvent effect, using the polarizable continuum model (PCM). The PCM and SAC/SAC-CI were consistently combined in terms of the energy functional formalism. The excitation energies were calculated by means of the state-specific approach, the advantage of which over the linear-response approach has been shown. The single-point energy calculation and its analytical energy derivatives are presented and implemented, where the free-energy and its derivatives are evaluated because of the presence of solute-solvent interactions. We have applied this method to s-trans-acrolein and metylenecyclopropene of their electronic excitation in solution. The molecular geometries in the ground and excited states were optimized in vacuum and in solution, and both the vertical and adiabatic excitations were studied. The PCM-SAC/SAC-CI reproduced the known trend of the solvent effect on the vertical excitation energies but the shift values were underestimated. The excited state geometry in planar and nonplanar conformations was investigated. The importance of using state-specific methods was shown for the solvent effect on the optimized geometry in the excited state. The mechanism of the solvent effect is discussed in terms of the Mulliken charges and electronic dipole moment.