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).

Text

** 19795.pdf
- Version of Record**
## More information

Published date: 8 November 2002

Keywords:
microwave-spectrum, wave-functions, alkali oxides, ab-initio, spectroscopy, lio, chemistry, nao, potassium, molecules

Organisations:
Chemistry

## Identifiers

Local EPrints ID: 19795

URI: http://eprints.soton.ac.uk/id/eprint/19795

ISSN: 0021-9606

PURE UUID: 37d12deb-6e79-4dfd-9deb-8a2fde64dfd0

## Catalogue record

Date deposited: 21 Feb 2006

Last modified: 08 Jan 2022 15:48

## Export record

## Altmetrics

## Contributors

Author:
Edmond P.F. Lee

Author:
Pavel Soldán

Author:
Timothy G. Wright

## Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics