Generalized Time-Dependent Approaches to Vibrationally Resolved Electronic and Raman Spectra: Theory and Applications

In this review, we summarize the computationally efficient time-dependent approaches to calculating the vibronic spectra including one-photon/two-photon absorption (OPA/TPA), emission, circular dichroism (CD), and resonance Raman/hyper-Raman scattering (RRS/RHRS) spectra with inclusion of the mode-mixing, Frank-Condon (FC) and Herzberg-Teller (HT) effects. At first, a unified dependency of spectral differential cross sections (SDCSs) on a generalized linear polarizability is derived in view of the relationship between SDCSs and the linear or nonlinear polarizabilities. Then, the Green's function technique is adopted to calculate the polarizability to avoid the tedious summation over the large number of vibrational states. To demonstrate the computational accuracy and efficiency, we apply the generalized time-dependent approaches to calculate the OPA(E)/TPA, RRS, and RHRS spectra of a series of radicals and organic molecules. The computational accuracy is demonstrated by a close comparison between the simulated spectra and the available experimental data. In the spectral calculations, we apply our recently developed analytical energy-derivative approaches for the excited states within the framework of time-dependent density functional theory (TDDFT) to calculate the electronic-structure parameters which enter the expressions of SDCSs, such as the excited-state geometries, energy gradient, harmonic vibrational frequencies, the geometrical derivatives of transition dipole moments, and so forth. It is found that the integrated approach which combines the time-dependent approach to SDCSs with the analytical energy-derivative approaches for TDDFT excited-state structure parameters breaks the bottlenecks of vibronic spectroscopy calculation down. (c) 2014 Wiley Periodicals, Inc.