Erratum to "Geometries and Vertical Excitation Energies in Retinal Analogues Resolved at the CASPT2 Level of Theory: Critical Assessment of the Performance of CASSCF, CC2, and DFT Methods".

Abstract

A systematic investigation of structural properties and vertical excitation energies of a series of structurally modified 11-cis-retinal chromophores in vacuo was performed by means of multiconfigurational second-order perturbation theory (CASPT2). CASPT2-based geometries agree reasonably well with Moller–Plesset second-order perturbation theory (MP2), local second-order approximate coupled cluster singles and doubles (LCC2), and density functional theory (DFT) geometries, while the complete active space self-consistent field (CASSCF) method exaggerates dramatically the bond length pattern in the polyene chain. The quality of the resulting vertical excitation energies obtained by employing CASSCF, second-order approximate coupled cluster singles and doubles (CC2), LCC2, and time-dependent density functional theory (TD-DFT) approaches is assessed with respect to the CASPT2 data. We show that the commonly used CASSCF/CASPT2 approach works reasonably well in the case of vertical excitation energies of planar...