Anharmonic excited state frequencies of para-difluorobenzene, toluene and catechol using analytic RI-CC2 second derivatives

Abstract

Analytic second nuclear derivatives for excited electronic state energies have been implemented for the resolution-of-the-identity accelerated CC2, CIS(D_∞) and ADC(2) models. Our efficient implementation with (²) memory demands enables the treatment of medium sized molecules with large basis sets and high numerical precision and thereby paves the way for semi-numerical evaluation of the higher-order derivatives required for anharmonic corrections to excited state vibrational frequencies. We compare CC2 harmonic and anharmonic excited state frequencies with experimental values for para-difluorobenzene, toluene and catechol. Basis set problems occur for out-of-plane bending vibrations due to intramolecular basis set superposition error. For non-planar molecules and in plane modes of planar molecules, the agreement between theory and experiment is better than 30 cm⁻¹ on average and we reassign a number of experimental bands on the basis of the ab initio predictions.