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Franck-Condon simulation of the photoelectron spectrum of AsCl(2) and the photodetachment spectrum of AsCl?2- employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl(2)

Franck-Condon simulation of the photoelectron spectrum of AsCl(2) and the photodetachment spectrum of AsCl?2- employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl(2)
Franck-Condon simulation of the photoelectron spectrum of AsCl(2) and the photodetachment spectrum of AsCl?2- employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl(2)
The currently most reliable theoretical estimates of the adiabatic ionization energies (AIE0) from the X?2B1 state of AsCl2 to the X?1A1 and ã3B1 states of AsCl, and the electron affinity (EA0) of AsCl2, including ?ZPE corrections, are calculated as 8.687(11), 11.320(23), and 1.845(12) eV, respectively (estimated uncertainties based on basis-set effects at the RCCSD(T) level). State-of-the-art ab initio calculations, which include RCCSD(T), CASSCF/MRCI, and explicitly correlated RHF/UCCSD(T)-F12x (x = a or b) calculations with basis sets of up to quintuple-zeta quality, have been carried out on the X?2B1 state of AsCl2, the X?1A1, ã3B1, and Ã1B1 states of AsCl, and the X?1A1 state of AsCl. Relativistic, core correlation and complete basis-set (CBS) effects have been considered. In addition, computed UCCSD(T)-F12a potential energy functions of relevant electronic states of AsCl2, AsCl, and AsCl were used to calculate Franck–Condon factors, which were then used to simulate the valence photoelectron spectrum of AsCl2 and the photodetachment spectrum of AsCl, both yet to be recorded. Lastly, we have also computed the AIE and EA values for NCl2, PCl2, and AsCl2 at the G4 level and for SbCl2 at the RCCSD(T)/CBS level. The trends in the AIE and EA values of the group V pnictogen dichlorides, PnCl2, where Pn = N, P, As, and Sb, were examined. The AIE and EA of PCl2 were found to be smaller than those of AsCl2, contrary to the order expected from the IE values of P and As.
ab initio calculations, franck–condon factors, photoelectron spectrum of ascl2, photodetachment of ascl, ie and ea of ascl2, aie and ea values of pnictogen dichlorides
1096-987X
1648-1660
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
CHAU, Foo-Tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
CHAU, Foo-Tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f

Mok, Daniel K.W., Lee, Edmond P.F., CHAU, Foo-Tim and Dyke, John M. (2011) Franck-Condon simulation of the photoelectron spectrum of AsCl(2) and the photodetachment spectrum of AsCl?2- employing UCCSD(T)-F12a potential energy functions: IE and EA of AsCl(2). Journal of Computational Chemistry, 32 (8), 1648-1660. (doi:10.1002/jcc.21743). (PMID:21328405)

Record type: Article

Abstract

The currently most reliable theoretical estimates of the adiabatic ionization energies (AIE0) from the X?2B1 state of AsCl2 to the X?1A1 and ã3B1 states of AsCl, and the electron affinity (EA0) of AsCl2, including ?ZPE corrections, are calculated as 8.687(11), 11.320(23), and 1.845(12) eV, respectively (estimated uncertainties based on basis-set effects at the RCCSD(T) level). State-of-the-art ab initio calculations, which include RCCSD(T), CASSCF/MRCI, and explicitly correlated RHF/UCCSD(T)-F12x (x = a or b) calculations with basis sets of up to quintuple-zeta quality, have been carried out on the X?2B1 state of AsCl2, the X?1A1, ã3B1, and Ã1B1 states of AsCl, and the X?1A1 state of AsCl. Relativistic, core correlation and complete basis-set (CBS) effects have been considered. In addition, computed UCCSD(T)-F12a potential energy functions of relevant electronic states of AsCl2, AsCl, and AsCl were used to calculate Franck–Condon factors, which were then used to simulate the valence photoelectron spectrum of AsCl2 and the photodetachment spectrum of AsCl, both yet to be recorded. Lastly, we have also computed the AIE and EA values for NCl2, PCl2, and AsCl2 at the G4 level and for SbCl2 at the RCCSD(T)/CBS level. The trends in the AIE and EA values of the group V pnictogen dichlorides, PnCl2, where Pn = N, P, As, and Sb, were examined. The AIE and EA of PCl2 were found to be smaller than those of AsCl2, contrary to the order expected from the IE values of P and As.

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More information

Published date: June 2011
Keywords: ab initio calculations, franck–condon factors, photoelectron spectrum of ascl2, photodetachment of ascl, ie and ea of ascl2, aie and ea values of pnictogen dichlorides

Identifiers

Local EPrints ID: 184805
URI: http://eprints.soton.ac.uk/id/eprint/184805
ISSN: 1096-987X
PURE UUID: 5a666b6c-0b58-4c07-b7fa-e12abb149141
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 09 May 2011 10:21
Last modified: 15 Mar 2024 02:35

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Contributors

Author: Daniel K.W. Mok
Author: Edmond P.F. Lee
Author: Foo-Tim CHAU
Author: John M. Dyke ORCID iD

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