What is the ground electronic state of KO?
What is the ground electronic state of KO?
High-level, restricted coupled cluster with singles, doubles, and perturbative triples calculations are performed to determine the ground electronic state of KO. In the absence of spin-orbit coupling, we find that the ground state is a (2)Sigma(+) state, with a (2)Pi state lying just over 200 cm(-1) higher in energy. We ascertain that basis set extension, higher-order correlation energy, mass-velocity, and Darwin relativistic terms do not change this ordering. We then calculate the low-lying Omega states when spin-orbit coupling is turned on. The (2)Sigma(1/2)(+) state undergoes an avoided crossing with the (2)Pi(1/2) state, and we therefore designate the ground state as X-1/2. This state is essentially (2)Sigma(1/2)(+) at short R, but essentially (2)Pi(1/2) at long R; there is a corresponding A 1/2 state with the opposite behavior. These states have significantly different shapes and so spectroscopy from the adiabatic states. Finally, we calculate the dissociation energy D-0, of KO as 66 +/- 1 kcal mol(-1) and derive DeltaH(f) (KO, 0 K) as 13.66 +/- 1 kcal mol(-1).
microwave-spectrum, wave-functions, alkali oxides, ab-initio, spectroscopy, lio, chemistry, nao, potassium, molecules
8241-8247
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Soldán, Pavel
a58f438f-bf0a-42bb-8efe-98c8d2eb6fbc
Wright, Timothy G.
20c2bf2d-6181-4571-9fdc-af171ad62cd5
8 November 2002
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Soldán, Pavel
a58f438f-bf0a-42bb-8efe-98c8d2eb6fbc
Wright, Timothy G.
20c2bf2d-6181-4571-9fdc-af171ad62cd5
Lee, Edmond P.F., Soldán, Pavel and Wright, Timothy G.
(2002)
What is the ground electronic state of KO?
Journal of Chemical Physics, 117 (18), .
(doi:10.1063/1.1511179).
Abstract
High-level, restricted coupled cluster with singles, doubles, and perturbative triples calculations are performed to determine the ground electronic state of KO. In the absence of spin-orbit coupling, we find that the ground state is a (2)Sigma(+) state, with a (2)Pi state lying just over 200 cm(-1) higher in energy. We ascertain that basis set extension, higher-order correlation energy, mass-velocity, and Darwin relativistic terms do not change this ordering. We then calculate the low-lying Omega states when spin-orbit coupling is turned on. The (2)Sigma(1/2)(+) state undergoes an avoided crossing with the (2)Pi(1/2) state, and we therefore designate the ground state as X-1/2. This state is essentially (2)Sigma(1/2)(+) at short R, but essentially (2)Pi(1/2) at long R; there is a corresponding A 1/2 state with the opposite behavior. These states have significantly different shapes and so spectroscopy from the adiabatic states. Finally, we calculate the dissociation energy D-0, of KO as 66 +/- 1 kcal mol(-1) and derive DeltaH(f) (KO, 0 K) as 13.66 +/- 1 kcal mol(-1).
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Published date: 8 November 2002
Keywords:
microwave-spectrum, wave-functions, alkali oxides, ab-initio, spectroscopy, lio, chemistry, nao, potassium, molecules
Organisations:
Chemistry
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Local EPrints ID: 19795
URI: http://eprints.soton.ac.uk/id/eprint/19795
ISSN: 0021-9606
PURE UUID: 37d12deb-6e79-4dfd-9deb-8a2fde64dfd0
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Date deposited: 21 Feb 2006
Last modified: 15 Mar 2024 06:19
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Author:
Edmond P.F. Lee
Author:
Pavel Soldán
Author:
Timothy G. Wright
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