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Ab initio calculations on SF2 and its low-lying cationic states: Anharmonic Franck-Condon simulation of the uv photoelectron spectrum of SF2

Ab initio calculations on SF2 and its low-lying cationic states: Anharmonic Franck-Condon simulation of the uv photoelectron spectrum of SF2
Ab initio calculations on SF2 and its low-lying cationic states: Anharmonic Franck-Condon simulation of the uv photoelectron spectrum of SF2
Geometry optimization calculations were carried out on the X (1)A(1) state of SF2 and the X B-2(1), A (2)A(1), B B-2(2), C B-2(2), D (2)A(1), and E (2)A(2) states of SF2+ employing the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] method and basis sets of up to the augmented correlation-consistent polarized quintuple-zeta [aug-cc-pV(5+d)Z] quality. Effects of core electron (S 2s(2)2p(6) and F 1s(2) electrons) correlation and basis set extension to the complete basis set limit on the computed minimum-energy geometries and relative electronic energies (adiabatic and vertical ionization energies) were investigated. RCCSD(T) potential energy functions (PEFs) were calculated for the X (1)A(1) state of SF2 and the low-lying states of SF2+ listed above employing the aug-cc-pV(5+d)Z and aug-cc-pV5Z basis sets for S and F, respectively. Anharmonic vibrational wave functions of these neutral and cationic states of SF2, and Franck-Condon (FC) factors of the lowest four one-electron allowed neutral photoionizations were computed employing the RCCSD(T) PEFs. Calculated FC factors with allowance for Duschinsky rotation and anharmonicity were used to simulate the first four photoelectron bands of SF2. The agreement between the simulated and observed first bands in the He I photoelectron spectrum reported by de Leeuw [Chem. Phys. 34, 287 (1978)] is excellent. Our calculations largely support assignments made by de Leeuw on the higher ionization energy bands of SF2.
enhanced multiphoton ionization, excited electronic states, lower chalcogen fluorides, sulfur difluoride, microwave-spectrum, infrared-spectrum, emission-spectrum, basis-sets, thermochemistry, energies
0021-9606
104304-[13pp]
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Chau, Foo-tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Chau, Foo-tim
e15ec394-d11b-4cbe-91f3-cdac037d9d0e
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f

Lee, Edmond P.F., Mok, Daniel K.W., Chau, Foo-tim and Dyke, John M. (2006) Ab initio calculations on SF2 and its low-lying cationic states: Anharmonic Franck-Condon simulation of the uv photoelectron spectrum of SF2. The Journal of Chemical Physics, 125 (10), 104304-[13pp]. (doi:10.1063/1.2227380). (PMID:1699952)

Record type: Article

Abstract

Geometry optimization calculations were carried out on the X (1)A(1) state of SF2 and the X B-2(1), A (2)A(1), B B-2(2), C B-2(2), D (2)A(1), and E (2)A(2) states of SF2+ employing the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] method and basis sets of up to the augmented correlation-consistent polarized quintuple-zeta [aug-cc-pV(5+d)Z] quality. Effects of core electron (S 2s(2)2p(6) and F 1s(2) electrons) correlation and basis set extension to the complete basis set limit on the computed minimum-energy geometries and relative electronic energies (adiabatic and vertical ionization energies) were investigated. RCCSD(T) potential energy functions (PEFs) were calculated for the X (1)A(1) state of SF2 and the low-lying states of SF2+ listed above employing the aug-cc-pV(5+d)Z and aug-cc-pV5Z basis sets for S and F, respectively. Anharmonic vibrational wave functions of these neutral and cationic states of SF2, and Franck-Condon (FC) factors of the lowest four one-electron allowed neutral photoionizations were computed employing the RCCSD(T) PEFs. Calculated FC factors with allowance for Duschinsky rotation and anharmonicity were used to simulate the first four photoelectron bands of SF2. The agreement between the simulated and observed first bands in the He I photoelectron spectrum reported by de Leeuw [Chem. Phys. 34, 287 (1978)] is excellent. Our calculations largely support assignments made by de Leeuw on the higher ionization energy bands of SF2.

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Published date: September 2006
Keywords: enhanced multiphoton ionization, excited electronic states, lower chalcogen fluorides, sulfur difluoride, microwave-spectrum, infrared-spectrum, emission-spectrum, basis-sets, thermochemistry, energies
Organisations: Chemistry

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Local EPrints ID: 174183
URI: http://eprints.soton.ac.uk/id/eprint/174183
ISSN: 0021-9606
PURE UUID: c1fff8df-062d-4759-bbf2-91cc8c222a67
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 11 Feb 2011 13:53
Last modified: 20 Jul 2019 01:27

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