Benchmarking CASPT3 Vertical Excitation Energies

Abstract

Based on 280 reference vertical transition energies of various natures (singlet, triplet, valence, Rydberg, $n\to {\pi }^{\ast }$, $\pi \to {\pi }^{\ast }$, and double excitations) extracted from the QUEST database, we assess the accuracy of third-order multireference 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 of the mean absolute error to $0.09$ eV when the IPEA shift is switched off.

Comments: 12 pages, 3 figures (supplementary material available)