title: PtF6(2-) dianion and its detachment spectrum: a fully relativistic study.
abstract: In this work we calculate the photoelectron spectrum of the PtF(6)2- dianion by application of the third-order Dirac-Hartree-Fock one-particle propagator technique. Relativistic effects and electron correlation are hereby treated on a consistent theoretical basis which is mandatory for systems containing heavy elements. A PtF6(2-) gas phase photoelectron spectrum is not yet available and our calculations therefore have predictive character. As it is characteristic for dianionic systems a strong dependence on basis set size and molecular geometry is observed. In contrast to the already calculated PtCl(6)2- photoelectron spectrum no valence orbital inversion due to strong interplay of spin-orbit coupling and electron correlation is observed. Furthermore an unusually strong spin-orbit splitting was found for the sigma-type subvalence 1t1u molecular spinor despite its very small platinum p population. The double ionization threshold is strongly lowered by relativistic effects now enabling an interatomic Coulombic decay process after ionization from the sigma-bonding orbitals. The results stress the importance of spin-orbit coupling for the understanding of the spectral structure which cannot be reproduced by a scalar-relativistic treatment only.
authors: Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. fMarkus.Pernpointner@pci.uni-heidelberg.de
authors: Markus
authors: M
authors: Pernpointner
authors: Lorenz S
authors: LS
authors: Cederbaum