A combined ab initio/Franck-Condon study of the Ã-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl

A combined ab initio/Franck-Condon study of the Ã-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl

State-of-the-art ab initio calculations have been carried out on the X(1)A(1), a(3)B(1) and A(1)B(1) states of CCl2 and the (XB1)-B-2 state of CCl2-. Franck-Condon factors including anhormonicity have been colculated, between the CCl2 states, and between the CCl2- (XB1)-B-2 state and the CCl2 states. They are used to simulate the A-X single-vibronic-level (SVL) emission spectra of CCl2 determined by MA. Lui et a]. [PCCP 2003, 5, 352] and the 364 nm laser photodetachment spectrum of CCl2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 7999, 103, 8213]. Comparison between simulated and observed spectra confirms the vibrational assignments of the (XB1)-B-2 SVL emission spectra and the T-0 position of the A(1)B(1) state of CCl2. For the photodetachment spectrum of CCl2-, spectral simulation shows that the higher binding energy 6 3 B, (CCl2) CCl2-((XB1)-B-2) detachment process. Further ab initio calculations carried out in the present investigation support the suggestion that the second band in the 364 nm photodetachment spectrum of CCl2- is due to detachment from an excited state of CCl2-, a linear quartet state, to a triplet state of CC12. These calculations identify the anionic state to be the lowest (4)Sigma(g)(-) ((4)Sigma(-)) state, which photodetaches vertically to the (3)Sigma(g)(-) ((3)Sigma(-); adiabatically a(3)B(1)) and/or (3)Pi(u) ((3)Pi) states of CCl2 to give the second band observed in the 364 nm photodetachment spectrum of CCl2-.

ab initio calculations, franck-condon factors, photochemistry, photoelectron spectroscopy, spectral simulationscorrelated molecular calculations, gaussian-basis sets, photoelectron-spectroscopy, excitation spectrum, atoms aluminum, free-jet, dichlorocarbene, argon, cf2, initio

2046-2059

Dyke, John M.

ffa1efaf-0eb1-4f69-94ef-b276534b5a57

Lee, Edmond P.F.

28f39876-705a-4fa5-b340-db5658ce1503

Mok, Daniel K.W.

49a4e516-0e71-4f59-a3ec-bd607b47ef33

Chau, Foo-tim

e15ec394-d11b-4cbe-91f3-cdac037d9d0e

14 October 2005

Dyke, John M.

ffa1efaf-0eb1-4f69-94ef-b276534b5a57

Lee, Edmond P.F.

28f39876-705a-4fa5-b340-db5658ce1503

Mok, Daniel K.W.

49a4e516-0e71-4f59-a3ec-bd607b47ef33

Chau, Foo-tim

e15ec394-d11b-4cbe-91f3-cdac037d9d0e

Dyke, John M., Lee, Edmond P.F., Mok, Daniel K.W. and Chau, Foo-tim
(2005)
A combined ab initio/Franck-Condon study of the Ã-X single-vibronic-level emission spectrum of CCl2 and the photodetachment spectrum of CCl.
*ChemPhysChem*, 6 (10), .
(doi:10.1002/cphc.200500194).

## Abstract

State-of-the-art ab initio calculations have been carried out on the X(1)A(1), a(3)B(1) and A(1)B(1) states of CCl2 and the (XB1)-B-2 state of CCl2-. Franck-Condon factors including anhormonicity have been colculated, between the CCl2 states, and between the CCl2- (XB1)-B-2 state and the CCl2 states. They are used to simulate the A-X single-vibronic-level (SVL) emission spectra of CCl2 determined by MA. Lui et a]. [PCCP 2003, 5, 352] and the 364 nm laser photodetachment spectrum of CCl2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 7999, 103, 8213]. Comparison between simulated and observed spectra confirms the vibrational assignments of the (XB1)-B-2 SVL emission spectra and the T-0 position of the A(1)B(1) state of CCl2. For the photodetachment spectrum of CCl2-, spectral simulation shows that the higher binding energy 6 3 B, (CCl2) CCl2-((XB1)-B-2) detachment process. Further ab initio calculations carried out in the present investigation support the suggestion that the second band in the 364 nm photodetachment spectrum of CCl2- is due to detachment from an excited state of CCl2-, a linear quartet state, to a triplet state of CC12. These calculations identify the anionic state to be the lowest (4)Sigma(g)(-) ((4)Sigma(-)) state, which photodetaches vertically to the (3)Sigma(g)(-) ((3)Sigma(-); adiabatically a(3)B(1)) and/or (3)Pi(u) ((3)Pi) states of CCl2 to give the second band observed in the 364 nm photodetachment spectrum of CCl2-.

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## More information

Published date: 14 October 2005

Keywords:
ab initio calculations, franck-condon factors, photochemistry, photoelectron spectroscopy, spectral simulationscorrelated molecular calculations, gaussian-basis sets, photoelectron-spectroscopy, excitation spectrum, atoms aluminum, free-jet, dichlorocarbene, argon, cf2, initio

## Identifiers

Local EPrints ID: 20785

URI: http://eprints.soton.ac.uk/id/eprint/20785

ISSN: 1439-4235

PURE UUID: a7f7b0aa-9df6-4cbc-8337-9c6bf371fb0f

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Date deposited: 03 Mar 2006

Last modified: 15 Jul 2019 19:25

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## Contributors

Author:
John M. Dyke

Author:
Edmond P.F. Lee

Author:
Daniel K.W. Mok

Author:
Foo-tim Chau

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