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Vibrationally resolved electronic absorption spectra including the effect ofvibrational pre-excitation are computed in order to interpret and predictvibronic transitions that are probed in the Vibrationally Promoted ElectronicResonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem.Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent andtime-dependent methods based on the evaluation of Franck-Condon overlapintegrals and Fourier transformation of time-domain wavepacket autocorrelationfunctions, respectively. The time-independent approach uses a generalizedversion of the FCclasses method [F. Santoro et al., J. Chem. Phys. 126, 084509(2007)]. In the time-dependent approach, autocorrelation functions are obtainedby wavepacket propagation and by evaluation of analytic expressions, within theharmonic approximation including Duschinsky rotation effects. For severalmedium-sized polyatomic systems, it is shown that selective pre-excitation ofparticular vibrational modes leads to a red-shift of the low-frequency edge ofthe electronic absorption spectrum, which is a prerequisite for the VIPERexperiment. This effect is typically most pronounced upon excitation of ringdistortion modes within an aromatic pi-system. Theoretical predictions as towhich modes show the strongest VIPER effect are found to be in excellentagreement with experiment.

Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy