Outer-core emission spectroscopy of the heavy alkaline-earth metals
Gutleben, Christian Daniel
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https://hdl.handle.net/2142/18912
Description
Title
Outer-core emission spectroscopy of the heavy alkaline-earth metals
Author(s)
Gutleben, Christian Daniel
Issue Date
1992
Doctoral Committee Chair(s)
Flynn, C.P.
Department of Study
Physics
Discipline
Physics
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
outer-core emission spectroscopy
heavy alkaline earth metals
optical emission spectra
core-excited configurations
Language
en
Abstract
Optical emission spectra from the np5 initial core-excited configurations of the
alkaline-earth metals calcium, strontium, and barium are presented. The spectra are
found to be anomalously broad and red-shifted with regard to XPS core positions. With
the help of data from complementary core-level spectroscopies, a model for both the
creation and the annihilation of these core configurations is inferred.
By considering the structure of the core-hole screening in a pseudo-atomic format,
the set of symmetry allowed recombination events is determined. The initial core-excited
configuration is found to involve a strongly local, d-like charge which is spin polarized
parallel to the core. Because the optical transition between this configuration and the
ground configuration is dipole forbidden, the emission spectra mainly reflect those
allowed transitions which leave the local environment in a valence-excited configuration.
The dynamics of the creation of the core-hole configuration are found to strongly
lll
influence both the photoelectron spectra and the optical absorption spectra for these
cores.
The optical emission spectra from alkaline-earths as impurities in alkali-metal host
lattices, show little modification from the pure metal spectra. The minor differences
which do occur upon dilution take the form of small chemical-shifts and some very slight
line-shape alterations. The alloys thus serve to illustrate the strongly local character of
these outer-core transitions. Beginning at very low alkaline impurity concentrations, in
contrast to the behavior of the alkaline bands, the emission bands associated with the
alkali host metals show both a strong quenching of the pure-metal x-ray edge peaks and
a substantial suppression of threshold emission intensity.
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