Impact of Interatomic Electronic Decay Processes on Xe 4d Hole Decay in the Xenon Fluorides

Abstract

A hole in a 4d orbital of atomic xenon relaxes through Auger decay after a lifetime of 3 fs. Adding electronegative fluorine ligands to form xenon fluoride molecules, results in withdrawal of valence-electron density from Xe. Thus, within the one-center picture of Auger decay, a lowered Xe 4d Auger width would be expected, in contradiction, however, with experiment. Employing extensive ab initio calculations within the framework of many-body Green's functions, we determine all available decay channels in XeFn and characterize these channels by means of a two-hole population analysis. We derive a relation between two-hole population numbers and partial Auger widths. On this basis, interatomic electronic decay processes are demonstrated to be so strong in the xenon fluorides that they overcompensate the reduction in intra-atomic Auger width and lead to the experimentally observed trend. The nature of the relevant processes is discussed. These processes presumably underlie Auger decay in a variety of systems.

11 pages, 5 figures, 3 tables, RevTeX4, extensively revised, the discussion of single ionization of XeFn was published separately: J. Chem. Phys. 119, 7763--7771 (2003), preprint arXiv: physics/0306123

References in corpus (4)

• Coulombic Energy Transfer and Triple Ionization in Clusters
• Ionization of the Xenon Fluorides
• Extended Two--Particle Green's Functions and Optical Potentials for Two--Particle Scattering by Many--Body Targets
• First Order Static Excitation Potential: Scheme for Excitation Energies and Transition Moments

Cited by in corpus (8)

• Ultrafast absorption of intense x rays by nitrogen molecules
• Non-Hermitian Rayleigh-Schroedinger Perturbation Theory
• Ab initio Green's function formalism for band structures
• Electron transfer mediated decay of alkali dimers attached to He nanodroplets
• Inner-shell photoionization and core-hole decay of Xe and XeF${}_2$
• Rate equations for nitrogen molecules in ultrashort and intense x-ray pulses
• Quasiparticle band structure of infinite hydrogen fluoride and hydrogen chloride chains
• Dissociating diatomic molecules in ultrafast and intense light