A theoretical study of the formation of benzene excimer: Effects of geometry relaxation and spin-state dependence

Abstract

Geometry relaxation effects on the formation of benzene excimer were investigated by means of ab initio calculation at SOS-CIS(D 0)/aug-cc-pVDZ level. In the case of T-shaped dimer configuration, intermolecular interactions in the excited states are found to be nearly the same as those in the ground state and structural deformations are limited within a single molecule; the geometry relaxation effects are then negligible and singlet-triplet energy gap remains constant. As for face-to-face eclipsed dimer, on the other hand, both molecules undergo structural change. As a result, intermolecular interactions in the excited states are significantly different than those in the ground state. Although the intermolecular distances obtained from potential energy curve calculation with frozen molecular structures are in qualitative agreement, the excited-state binding energies are notably overestimated with respect to those at optimized structures. In particular, the effects are calculated to be larger in T1 state and hence singlet-triplet energy gap, which reduces markedly in this configuration, is underestimated without relaxation.