Vibronic induced one- and two-photon absorption in a charge-transfer stilbene derivate

Both the electronic and the vibronic contributions to one-, and two-photon absorption of a D-p-D charge-transfer molecule (4-dimethylamino-4’-methyl-trans stilbene) are studied by means of density functional response theory combined with a linear coupling model. Vibronic profiles of the first four excited states are fully explored. The dominating vibrational modes for both Franck-Condon and Herzberg-Teller contributions are identified. The Franck-Condon contribution dominates the spectra of first, second and fourth excited states. The Herzberg-Teller contribution is on the other hand of comparable size for the third excited state, where its inclusion leads to a blue-shift with respect to the vertical transition. A similar vibronic coupling behavior is found for both one- and two-photon absorptions.