Simulation of x-ray absorption near edge spectra of electronically excited ruthenium tris-2,2'-bipyridine

The L3 edge x-ray absorption near edge spectrum (XANES) of the ground electronic state and the metal to ligand charge transfer state of ruthenium tris-2,2'-bipyridine is calculated. The final valence states and energies in the presence of the photoelectron and core hole, and the corresponding transition intensities are computed using time dependent density functional theory with the Becke three-parameter density functional with the Lee-Yang-Parr correlation functional. Calculations show a valence shift of the primary XANES peak and the appearance of the new XANES transition to the hole created by the optical excitation, in agreement with experiment [M. Saes, C. Bressler, R. Abela, D. Grolimund, S. L. Johnson, P. A. Heimann, and M. Chergui, Phys. Rev. Lett. 90, 047403 (2003)]