title: Time-Dependent Approach to Resonance Raman Spectra Including Duschinsky Rotation and Herzberg-Teller Effects: Formalism and Its Realistic Applications.
abstract: Efficient quantum dynamical and electronic structure approaches are presented to calculate resonance Raman spectroscopy (RRS) with inclusion of Herzberg-Teller (HT) contribution and mode-mixing (Duschinsky) effect. In the dynamical method, an analytical expression for RRS in the time domain is proposed to avoid summation over the large number of intermediate vibrational states. In the electronic structure calculations, the analytic energy-derivative approaches for the excited states within the time-dependent density functional theory (TDDFT), developed by us, are adopted to overcome the computational bottleneck of excited-state gradient and Hessian calculations. In addition, an analytic calculation to the geometrical derivatives of the transition dipole moment, entering the HT term, is also adopted. The proposed approaches are implemented to calculate RR spectra of a few of conjugated systems, phenoxyl radical, 2-thiopyridone in water solution, and free-base porphyrin. The calculated RR spectra show the evident HT effect in those π-conjugated systems, and their relative intensities are consistent with experimental measurements.
authors.affiliation: Hefei National Laboratory for Physical Science at Microscale, and Department of Chemical Physics, University of Science and Technology of China , Hefei 230026, People's Republic of China.
authors.forename: Huili
authors.initials: H
authors.lastname: Ma
authors.affiliation: Hefei National Laboratory for Physical Science at Microscale, and Department of Chemical Physics, University of Science and Technology of China , Hefei 230026, People's Republic of China.
authors.forename: Jie
authors.initials: J
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Xiamen University , Xiamen 361005, People's Republic of China.
authors.forename: WanZhen
authors.initials: W
authors.lastname: Liang