Christian Buth, Robin Santra, Lorenz S. Cederbaum — Theoretische Chemie, Physikalisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 229, 69120 Heidelberg, Germany
The decay of Xe 4d core ionized xenon fluorides (XeFx, x=2,4,6) is studied. The single and double ionization potentials are calculated and energetically accessible decay channels are identified. A connection between population analysis and decay width is shown. With this relation it can be argumented that certain electronic decay processes, formerly observed in inner valence ionized clusters, may increase the decay width of the xenon with increasing number of fluorines. These new decay processes are intramolecular interatomic Coulombic decay (IICD), two- and three-atomic intramolecular electron transfer mediated decay (IETMD).
The problem of the calculation of decay widths is addressed next. Here the focus is centered on excited rather than ionized molecules because this is a more general approach. Wigner-Weisskopf theory is applied to this issue and the resulting decay matrix elements are discussed. Afterwards a complex absorbing potential (CAP) is introduced to render the continuum problem square integrable. Then time-independent non-degenerate perturbation theory is applied and the relation to Wigner-Weisskopf theory is shown. The time-independent approach is generalised further in a non-Hermitian multireference perturbation theory. There the configuration interaction (CI) matrix is partitioned using projection operators and the complement space is coupled perturbatively to the reference space.
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Christian Buth
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