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Updated: Aug 19, 2026

Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−
Published on: July 27, 2018
Remarkable interplay of electron correlation and relativity in the photodetachment spectrum of PtCl(6)2-
Markus Pernpointner1, Jörg Breidbach, Lorenz S Cederbaum
1Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany. Markus.Pernpointer@pci.uni-heidelberg.de
Abstract:
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.
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