Benchmarking CASPT3 vertical excitation energies

Abstract

Based on 280 reference vertical transition energies of various excited states (singlet, triplet, valence, Rydberg, n → π*, π → π*, and double excitations) extracted from the QUEST database, we assess the accuracy of complete-active-space third-order perturbation theory (CASPT3), in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of 0.11 eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction in the mean absolute error to 0.09 eV when the IPEA shift is switched off.