General Time Dependent Approach to Vibronic Spectroscopy Including Franck-Condon, Herzberg-Teller, and Duschinsky Effects

摘要

An effective time-dependent (TD) approach to compute vibrationally resolved optical spectra from first principles is presented for the computation of one-photon electronic spectra induced by either electric or magnetic transition dipoles or by their mutual interaction, namely absorption, emission, and circular dichroism. Particular care has been devoted to generality, modularity, and numerical stability including all the contributions that play a role at the harmonic level of approximation, namely Franck—Condon, Herzberg—Teller, and Dushinsky (i.e., mode mixing) effects. The implementation shares the same general framework of our previous time-independent (TI) model, thus allowing an effective integration between both approaches with the consequent enhancement of their respective strengths (e.g., spectrum completeness and straightforward account of temperature effects for the TD route versus band resolution and assignment for the TI route) using a single set of starting data. Implementation of both models in the same general computer program allows comprehensive studies using several levels of electronic structure description together with effective account of environmental effects by atomistic and/or continuum models of different sophistication. A few medium-size molecules (furan, phenyl radical, anthracene, dimethyloxirane, coumarin 339) have been studied in order to fully validate the approach.