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An ab initio study on SnCl2 and Franck-Condon factor simulations of its a-X and B-X absorption and single-vibronic level emission spectra

An ab initio study on SnCl2 and Franck-Condon factor simulations of its a-X and B-X absorption and single-vibronic level emission spectra
An ab initio study on SnCl2 and Franck-Condon factor simulations of its a-X and B-X absorption and single-vibronic level emission spectra
Minimum-energy geometries, harmonic vibrational frequencies, and relative electronic energies of some low-lying singlet and triplet electronic states of stannous dichloride, SnCl2, have been computed employing the complete-active-space self-consistent-field/multireference configuration interaction (CASSCF/MRCI) and/or restricted-spin coupled-cluster single-double plus perturbative triple excitations [RCCSD(T)] methods. The small core relativistic effective core potential, ECP28MDF, was used for Sn in these calculations, together with valence basis sets of up to augmented correlation-consistent polarized-valence quintuple-zeta (aug-cc-pV5Z) quality. Effects of outer core electron correlation on computed geometrical parameters have been investigated, and contributions of off-diagonal spin-orbit interaction to relative electronic energies have been calculated. In addition, RCCSD(T) or CASSCF/MRCI potential energy functions of the 1A1, ã 3B1, and 1B1 states of SnCl2 have been computed and used to calculate anharmonic vibrational wave functions of these three electronic states. Franck-Condon factors between the 1A1 state, and the ã 3B1 and 1B1 states of SnCl2, which include anharmonicity and Duschinsky rotation, were then computed, and used to simulate the ã- and - absorption and corresponding single-vibronic-level emission spectra of SnCl2 which are yet to be recorded. It is anticipated that these simulated spectra will assist spectroscopic identification of gaseous SnCl2 in the laboratory and/or will be valuable in in situ monitoring of SnCl2 in the chemical vapor deposition of SnO2 thin films in the semiconductor gas sensor industry by laser induced fluorescence and/or ultraviolet absorption spectroscopy, when a chloride-containing tin compound, such as tin dichloride or dimethyldichlorotin, is used as the tin precursor.
photoelectron-spectroscopy, triplet energy separations, including anharmonicity, gas-phase, dispersed fluorescence spectroscopy, laser-induced fluorescence, vibrational frequencies, electronic spectroscopy, ionization-potentials, plasmas, fluorocarbon
0021-9606
024308-024323
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Chow, Wan-ki
64850617-fabf-442b-ab44-667bd4d5aa2e
Chau, Foo-tom
97db4b11-df6a-417b-a164-ff89fab8de05
Lee, Edmond P.F.
f47c6d5d-2d1f-4f03-a3ff-03658812d80b
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Mok, Daniel K.W.
49a4e516-0e71-4f59-a3ec-bd607b47ef33
Chow, Wan-ki
64850617-fabf-442b-ab44-667bd4d5aa2e
Chau, Foo-tom
97db4b11-df6a-417b-a164-ff89fab8de05

Lee, Edmond P.F., Dyke, John M., Mok, Daniel K.W., Chow, Wan-ki and Chau, Foo-tom (2007) An ab initio study on SnCl2 and Franck-Condon factor simulations of its a-X and B-X absorption and single-vibronic level emission spectra. The Journal of Chemical Physics, 127 (2), 024308-024323. (doi:10.1063/1.2749508).

Record type: Article

Abstract

Minimum-energy geometries, harmonic vibrational frequencies, and relative electronic energies of some low-lying singlet and triplet electronic states of stannous dichloride, SnCl2, have been computed employing the complete-active-space self-consistent-field/multireference configuration interaction (CASSCF/MRCI) and/or restricted-spin coupled-cluster single-double plus perturbative triple excitations [RCCSD(T)] methods. The small core relativistic effective core potential, ECP28MDF, was used for Sn in these calculations, together with valence basis sets of up to augmented correlation-consistent polarized-valence quintuple-zeta (aug-cc-pV5Z) quality. Effects of outer core electron correlation on computed geometrical parameters have been investigated, and contributions of off-diagonal spin-orbit interaction to relative electronic energies have been calculated. In addition, RCCSD(T) or CASSCF/MRCI potential energy functions of the 1A1, ã 3B1, and 1B1 states of SnCl2 have been computed and used to calculate anharmonic vibrational wave functions of these three electronic states. Franck-Condon factors between the 1A1 state, and the ã 3B1 and 1B1 states of SnCl2, which include anharmonicity and Duschinsky rotation, were then computed, and used to simulate the ã- and - absorption and corresponding single-vibronic-level emission spectra of SnCl2 which are yet to be recorded. It is anticipated that these simulated spectra will assist spectroscopic identification of gaseous SnCl2 in the laboratory and/or will be valuable in in situ monitoring of SnCl2 in the chemical vapor deposition of SnO2 thin films in the semiconductor gas sensor industry by laser induced fluorescence and/or ultraviolet absorption spectroscopy, when a chloride-containing tin compound, such as tin dichloride or dimethyldichlorotin, is used as the tin precursor.

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Published date: July 2007
Keywords: photoelectron-spectroscopy, triplet energy separations, including anharmonicity, gas-phase, dispersed fluorescence spectroscopy, laser-induced fluorescence, vibrational frequencies, electronic spectroscopy, ionization-potentials, plasmas, fluorocarbon
Organisations: Chemistry

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Local EPrints ID: 174175
URI: http://eprints.soton.ac.uk/id/eprint/174175
ISSN: 0021-9606
PURE UUID: a426ce15-11b8-43a4-9720-76a9b05125e5
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

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Date deposited: 11 Feb 2011 11:45
Last modified: 15 Mar 2024 02:35

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Contributors

Author: Edmond P.F. Lee
Author: John M. Dyke ORCID iD
Author: Daniel K.W. Mok
Author: Wan-ki Chow
Author: Foo-tom Chau

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