Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations
Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations
The heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) have been studied by high-level ab initio calculations. The RCCSD(T) method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a (2)Pi ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from (2)Pi to (2)Sigma(+) as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest (3)Sigma(-) and (3)Pi states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.
microwave-spectrum, ionization energies, diatomic-molecules, ground-state, ab-initio, spectroscopy, lio, thermodynamics, (2)sigma(+), explanation
Lee, Edmond P. F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Wright, Timothy G.
20c2bf2d-6181-4571-9fdc-af171ad62cd5
8 October 2005
Lee, Edmond P. F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Wright, Timothy G.
20c2bf2d-6181-4571-9fdc-af171ad62cd5
Lee, Edmond P. F. and Wright, Timothy G.
(2005)
Heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) and their cations.
The Journal of Chemical Physics, 123 (14).
Abstract
The heavier alkali-metal monosulfides (KS, RbS, CsS, and FrS) have been studied by high-level ab initio calculations. The RCCSD(T) method has been employed, combined with large flexible valence basis sets. All-electron basis sets are used for potassium and sulfur, with effective core potentials being used for the other metals, describing the core electrons. Potential-energy curves are calculated for the lowest two neutral and cationic states: all neutral monosulfide species have a (2)Pi ground state, in contrast with the alkali-metal monoxide species, which undergo a change in the electronic ground state from (2)Pi to (2)Sigma(+) as the group is descended. In the cases of KS, RbS, and CsS, spin-orbit curves are also calculated. We also calculate potential-energy curves for the lowest (3)Sigma(-) and (3)Pi states of the cations. From the potential-energy curves, spectroscopic constants are derived, and for KS the spectroscopic results are compared to experimental spectroscopic values. Ionization energies, dissociation energies, and heats of formation are also calculated; for KS, we explore the effects of relativity and basis set extrapolation on these values.
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Published date: 8 October 2005
Keywords:
microwave-spectrum, ionization energies, diatomic-molecules, ground-state, ab-initio, spectroscopy, lio, thermodynamics, (2)sigma(+), explanation
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Local EPrints ID: 20845
URI: http://eprints.soton.ac.uk/id/eprint/20845
ISSN: 0021-9606
PURE UUID: 6692ad66-2fb2-4fb4-96fe-324d6cac7396
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Date deposited: 02 Mar 2006
Last modified: 15 Mar 2024 06:26
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Author:
Edmond P. F. Lee
Author:
Timothy G. Wright
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