A fully relativistic study of the Pt(CN)42- and Pt(CN)62- photodetachment spectra

In this work the photoelectron spectra of the doubly charged transition metal complexes Pt(CN)42- and Pt(CN)62- are calculated by application of the one-particle propagator method in a fully relativistic framework. In systems with highly relativistic atoms spin-orbit coupling, electron correlation and scalar relativistic effects are hereby coupled in an intricate way and need to be treated consistently in order to obtain accurate results. The obtained ionization spectra are in very good agreement to experiment and the first ionization potentials were calculated as 1.40 eV for Pt(CN)42- and 4.00 eV for Pt(CN)62- compared to the experimental values of 1.69 eV and 4.01 eV [X.B. Wang, Y.L. Wang, H.K. Woo, J. Li, G.S. Wu, L.S. Wang, Chem. Phys. 329 (2006) 230].