Account of non-Condon effects in time-independent Raman wavefunction theory: Calculation of the S1← S0 vibronic absorption spectrum of formaldehyde.

Abstract

The time-independent eigenstate-free Raman wavefunction approach for calculating anharmonic vibronic spectra has been extended for the calculation of Herzberg-Teller contributions on the basis of an n-mode expansion of the transition electric dipole moment surface. This allows for the efficient simulation of Franck-Condon dark vibronic spectra. In addition, vibrational angular momentum terms have been implemented into this formalism, as they are important for an accurate description of vibrational wavefunctions spanning double-well potentials. This approach has been used to compute the FC-forbidden vibronic spectrum of the n → π* transition of formaldehyde based on a potential energy and transition dipole moment surfaces obtained from explicitly correlated multi-reference configuration interaction calculations. An extensive analysis of the resulting vibronic structure is provided, which allows for a detailed assignment and interpretation of the experimental spectrum.