Time-dependent density functional theory calculations of near-edge X-ray absorption fine structure with short-range corrected functionals

Besley, Nicholas A. and Peach, Michael J. G. and Tozer, David J. (2009) Time-dependent density functional theory calculations of near-edge X-ray absorption fine structure with short-range corrected functionals. Physical Chemistry Chemical Physics, 11 (44). pp. 10350-10358. ISSN 1463-9076

Abstract

We report calculations of core excitation energies and near-edge X-ray absorption fine structure (NEXAFS) spectra computed with time-dependent density functional theory (TDDFT). TDDFT with generalized gradient approximation and standard hybrid exchange-correlation functionals is known to underestimate core excitation energies. This failure is shown to be associated with the self-interaction error at short interelectronic distances. Short-range corrected hybrid functionals are shown to reduce the error in the computed core excitation energies for first and second row nuclei in a range of molecules to a level approaching that observed in more traditional excited states calculations in the ultraviolet region. NEXAFS spectra computed with the new functionals agree well with experiment and the pre-edge features in the NEXAFS spectra of plastocyanin are correctly predicted.