Theoretical Assessment of Excited State Gradients and Resonance Raman Intensities for the Azobenzene Molecule.

The ground state geometries and vibrational frequencies as well as the excitation energies and excited state gradients of the S(nπ*) and S(ππ*) states of trans- and cis-azobenzene are investigated by several DFT methods, namely B3LYP, PBE, M06-2X, CAM-B3LYP, and ωB97X. Excited state properties and in particular gradients are also assessed using the wave function based methods EOM-CCSD and RASPT2/RASSCF. Comparison with experimental data shows that the B3LYP functional gives the most accurate results for the ground state geometry and vibrational frequencies. The analysis of the vertical excitation energies reveals that the RASPT2 approach provides the most accurate excitation energies with deviations of the order of 0.1 eV. Among the TDDFT methods, the CAM-B3LYP functional shows the best performance on the excitation energies. By assessing the excited state gradients with respect to the reference RASPT2 data, the most accurate gradients are obtained with B3LYP, whereas other functionals as well as the EOM-CCSD and RASSCF calculations give less consistent results. Overall, despite the tendency of B3LYP to underestimate the excitation energies, this functional provides the most balanced description of both ground and excited state properties for both isomers of azobenzene in the Franck-Condon region.