Calculating X-ray Absorption Spectra of Open-Shell Molecules with the Unrestricted Algebraic-Diagrammatic Construction Scheme for the Polarization Propagator.

Abstract

X-ray absorption spectroscopy (XAS) is a powerful tool that provides information about the electronic structure of molecules via excitation of electrons from the K-shell core region to the unoccupied molecular levels. These high-lying electronic core-excited states can be accurately calculated using the algebraic-diagrammatic construction scheme of second order ADC(2) by applying the core-valence separation (CVS) approximation to the ADC(2) working equations. For the first time, an efficient implementation of an unrestricted CVS-ADC(2) variant CVS-UADC(2) is presented for the calculation of open-shell molecules by treating α and β spins separately from each other. The potential of the CVS-UADC(2) method is demonstrated with a set of small organic radicals by comparison with standard TD-DFT/B3LYP values and experimental data. It turns out that the extended variant CVS-UADC(2)-x, in particular, provides the most accurate results with errors of only 0.1% compared to experimental values. This remarkable agreement justifies the prediction of yet nonrecorded experimental XAS spectra like the one of the anthracene cation. The cation exhibits additional peaks due to the half-filled single-occupied molecular orbital, which may help to distinguish cation from the neutral species.