We present an ab initio computational
study of
the Auger spectra of methane, ethane, ethylene, and acetylene. Auger
spectroscopy is an established technique to probe the electronic structure
of molecules and exploits the Auger–Meitner effect that core-ionized
states undergo. We compute partial decay widths using coupled-cluster
theory with single and double substitutions (CCSD) and equation-of-motion
CCSD theory combined with complex-scaled basis functions and Feshbach–Fano
projection. We generate Auger spectra from these partial widths and
draw conclusions about the strength of particular decay channels and
trends among the four molecules. A connection to experimental results
about fragmentation pathways of the electronic states produced by
Auger decay is also made.
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We present an ab initio computational study of the Auger spectra of methane, ethane, ethylene, and acetylene. Auger spectroscopy is a established technique to probe the electronic structure of molecules and exploits the Auger-Meitner effect that coreionized states produced by X-ray irradiation undergo. We compute partial decay widths for the relevant decay channels using coupled-cluster theory with single and double substitutions (CCSD) and equation-of-motion-CCSD theory combined with complex-scaled basis functions and Feshbach-Fano projection. We generate Auger spectra from these partial widths and draw conclusions about the strength of particular decay channels and trends between the four molecules. A connection to experimental results about fragmentation pathways of the electronic states produced by Auger decay is also made.
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Auger decay is a relaxation process of core-vacant states in atoms and molecules, in which one valence electron fills the core vacancy while a second one is emitted. These states pose a challenge to electronic-structure theory, because they are embedded in the ionization continuum. Recently, we showed that molecular Auger decay can be described using complex-variable coupled-cluster (CC) methods and that partial widths and branching ratios can be computed based on a decomposition of the CC energy. Here, we introduce channel-specific core-valence projectors, dubbed Auger channel projectors, as a more general technique to evaluate partial widths from complex-variable treatments. We apply this new method to core-ionized states of neon, water, ammonia, and methane using CC singles and doubles (CCSD), equation-of-motion ionization potential CCSD, and configuration interaction singles (CIS) wave functions. Even though a single CIS calculation can never describe all Auger decay channels at once, we show that a combination of CIS calculations based on different reference states is able to recover partial and total decay widths from CC calculations to an excellent degree.
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AbstractIn a bold legislative move, in 2009 Germany introduced a fundamental reform of the government borrowing rules which are specified in its constitution. In particular, state governments will be required to provide a balanced budget, abstracting from cyclical fluctuations, starting in the year 2020. A fundamental requirement for the practical implementation of such a rule is the unequivocal decomposition of the actual budget surplus or deficit into derived structural and cyclical components. This paper uses an approach designed to identify cyclical components which tend to average out over time, and calculates the corresponding current structural deficits of all 16 federal states. We find that, at the time being, only two federal states have exerted sufficient effort to reduce their structural deficits to an extent which would be fully compatible with the objective of adhering to the constitutional rules at the end of this decade.JEL Classification: H61, H62, H72, H74.Rheinisch-Westfälisches Institut für Wirtschaftsforschung (RWI), Hohenzollernstraße 1-3,
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