On the TD-DFT Accuracy in Determining Single and Double Bonds in Excited-State Structures of Organic Molecules

Abstract

We present an analysis on the behavior of the TD-DFT approach in the determination of excited-state structures with particular attention to single and double bonds. The analysis is based on a direct comparison with the highly correlated CASPT2 ab initio approach. Six DFT exchange-correlation functionals differing in the Hartree-Fock exchange percentage and the type of correlation functional are considered and applied to the study of seven prototype organic molecules characterized by two families of excitations (acrolein, acetone, diazomethane, and propanoic acid anion for n-π* and cis-1,3-butadiene, trans-1,3-butadiene, and pyrrole for π-π*), and three protonated Schiff bases, used as model chromophores for 11-cis retinal. Our analysis allows pinpointing specific correlations between accuracy of the various functionals and category of excitation and/or type of chemical bond involved in the corresponding geometry relaxation. We confirm the role of the long-range correction of the potential to obtain a balanced description of excitation energies and excited-state structures, but we also point out that, for a small system, B3LYP and PBE0 also give results close to CASPT2.