Remarkable interplay of electron correlation and relativity in the photodetachment spectrum of PtCl(6)2-.
In this work we calculate the photoelectron spectrum of the PtCl(6) (2-) dianion by application of the recently developed third-order Dirac-Hartree-Fock implementation of the one-particle propagator technique allowing for a consistent treatment of spin-orbit and scalar relativistic effects together with electron correlation. For PtCl(6) (2-) a gas phase photoelectron spectrum is available showing clearly discernible structures not reproducible by a nonrelativistic or purely scalar-relativistic computation. A population analysis of the valence orbitals allows for an assignment of the photoelectron peaks and reveals the strong influence of relativity in combination with electron correlation.
Pernpointner
Markus
M
Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. Markus.Pernpointer@pci.uni-heidelberg.de
Breidbach
Jörg
J
Cederbaum
Lorenz S
LS