Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

J. A. Schmidt; J. M. H. Olsen

doi:10.1063/1.4901426

Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

J. A. Schmidt, J. M. H. Olsen

Kemisk Institut

14 Citationer (Scopus)

Abstract

The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys.136, 131101 (2012);J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys.137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 21 A ′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys.138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 11 A ″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys.138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO.

Originalsprog	Engelsk
Artikelnummer	184310
Tidsskrift	Journal of Chemical Physics
Vol/bind	141
Udgave nummer	18
ISSN	0021-9606
DOI	https://doi.org/10.1063/1.4901426
Status	Udgivet - 14 nov. 2014

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title = "Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects",

abstract = "The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 21A′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 11A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO. crossmark REFERENCES S. A. Montzka, P. Calvert, B. D. Hall, J. W. Elkins, T. J. Conway, P. P. Tans, and C. Sweeney, J. Geophys. Res. 112, D09302, doi:10.1029/2006JD007665 (2007).",

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T2 - Deviations between theory and experiment, and the importance of higher order correlation effects

AU - Schmidt, J. A.

AU - Olsen, J. M. H.

PY - 2014/11/14

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N2 - The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 21A′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 11A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO. crossmark REFERENCES S. A. Montzka, P. Calvert, B. D. Hall, J. W. Elkins, T. J. Conway, P. P. Tans, and C. Sweeney, J. Geophys. Res. 112, D09302, doi:10.1029/2006JD007665 (2007).

AB - The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 21A′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 11A″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO. crossmark REFERENCES S. A. Montzka, P. Calvert, B. D. Hall, J. W. Elkins, T. J. Conway, P. P. Tans, and C. Sweeney, J. Geophys. Res. 112, D09302, doi:10.1029/2006JD007665 (2007).

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DO - 10.1063/1.4901426

M3 - Journal article

C2 - 25399150

SN - 0021-9606

VL - 141

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

IS - 18

M1 - 184310

ER -

Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

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