Rotationally averaged linear absorption spectra beyond the electric-dipole approximation
Résumé
Based on the recently developed implementation of the full semi-classical field-matter interaction operator [List et al. in J. Chem. Phys. 142, 244111 (2015)], we present a numerically accurate yet efficient scheme to perform rotational averaging of linear absorption spectra beyond the electric-dipole approximation. This allows for a gauge-origin independent determination of UV/vis and X-ray absorption spectra for randomly oriented systems such as multilayers, liquids, and gas phase samples. The approach is illustrated by the determination of spectral intensities of electric-dipole allowed π → π * transitions and electric-dipole forbidden n → π * transitions in the UV-vis region of the spectrum as well as electric-dipole forbidden 1s → 3d transitions in the X-ray region of the spectrum. The employed Lebedev quadrature scheme shows very fast convergence with respect to the number of symmetry-independent quadrature points-in all considered cases, the oscillator strengths for the randomly oriented systems are fully converged with use of only seven quadrature points.
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