Time Dependent Density Functional Theory description of giant resonances in transition metal complexes: The photoionization dynamics of Cr(CO)6

The photoionization dynamics of Cr(CO)(6) has been calculated at the TDDFT level, employing a basis set of multicentric B-spline functions with the explicit treatment of the photoelectron continuum. The cross section and the asymmetry parameter profiles of all the valence orbitals have been considered and compared with the available experimental data. The most interesting spectral feature is the intense autoionization resonance Cr 3p -> Cr 3d observed in the experiment of band A, which is very well reproduced by present calculation at the TDDFT level. Other observed spectral features have been ascribed to shape resonances and assigned according to the dipole-prepared continuum orbital nature. The present TDDFT scheme proves accurate and practicable on large and complex systems containing transition metal compounds, for the description and the interpretation of the photoionization dynamics. (C) 2009 Elsevier B.V. All rights reserved.