The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field
A new quartic force field for the SO[subscript 2] C̃ [superscript 1]B[subscript 2] state has been derived, based on high resolution data from S[superscript 16]O[subscript 2] and S[superscript 18]O[subscript 2]. Included are eight b[subscript 2] symmetry vibrational levels of S[superscript 16]O[subsc...
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| Format: | Article |
| Language: | en_US |
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American Institute of Physics (AIP)
2017
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| Online Access: | http://hdl.handle.net/1721.1/110608 https://orcid.org/0000-0002-3526-3797 https://orcid.org/0000-0002-7609-4205 |
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| author | Jiang, Jun Park III, George Barratt Field, Robert W |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Jiang, Jun Park III, George Barratt Field, Robert W |
| author_sort | Jiang, Jun |
| collection | MIT |
| description | A new quartic force field for the SO[subscript 2] C̃ [superscript 1]B[subscript 2] state has been derived, based on high resolution data from S[superscript 16]O[subscript 2] and S[superscript 18]O[subscript 2]. Included are eight b[subscript 2] symmetry vibrational levels of S[superscript 16]O[subscript 2] reported in the first paper of this series [G. B. Park et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C̃ state vibrational levels, are well reproduced using our force field. Because the two stretching modes of the C̃ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C̃ state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and Xiao [J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm[superscript −1]. Based on our force field, the structure of the Coriolis interactions in the C̃ state of SO[subscript 2] is also discussed. We identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, νβ (which correlates with the antisymmetric stretching mode in our assignment scheme). |
| first_indexed | 2024-09-23T10:40:11Z |
| format | Article |
| id | mit-1721.1/110608 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:40:11Z |
| publishDate | 2017 |
| publisher | American Institute of Physics (AIP) |
| record_format | dspace |
| spelling | mit-1721.1/1106082024-07-11T19:49:29Z The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field The Rotation-Vibration Structure of the SO2 C˜ 1B2 State Explained by a New Internal Coordinate Force Field Jiang, Jun Park III, George Barratt Field, Robert W Massachusetts Institute of Technology. Department of Chemistry Jiang, Jun Park III, George Barratt Field, Robert W A new quartic force field for the SO[subscript 2] C̃ [superscript 1]B[subscript 2] state has been derived, based on high resolution data from S[superscript 16]O[subscript 2] and S[superscript 18]O[subscript 2]. Included are eight b[subscript 2] symmetry vibrational levels of S[superscript 16]O[subscript 2] reported in the first paper of this series [G. B. Park et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C̃ state vibrational levels, are well reproduced using our force field. Because the two stretching modes of the C̃ state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C̃ state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and Xiao [J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm[superscript −1]. Based on our force field, the structure of the Coriolis interactions in the C̃ state of SO[subscript 2] is also discussed. We identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, νβ (which correlates with the antisymmetric stretching mode in our assignment scheme). 2017-07-10T19:59:01Z 2017-07-10T19:59:01Z 2016-04 2016-03 Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/110608 Jiang, Jun, G. Barratt Park, and Robert W. Field. “The Rotation-Vibration Structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] State Explained by a New Internal Coordinate Force Field.” The Journal of Chemical Physics 144.14 (2016): 144312. https://orcid.org/0000-0002-3526-3797 https://orcid.org/0000-0002-7609-4205 en_US http://dx.doi.org/10.1063/1.4945621 The Journal of Chemical Physics Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf American Institute of Physics (AIP) arXiv |
| spellingShingle | Jiang, Jun Park III, George Barratt Field, Robert W The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title | The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title_full | The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title_fullStr | The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title_full_unstemmed | The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title_short | The rotation-vibration structure of the SO[subscript 2] C̃[superscript 1]B[subscript 2] state explained by a new internal coordinate force field |
| title_sort | rotation vibration structure of the so subscript 2 c superscript 1 b subscript 2 state explained by a new internal coordinate force field |
| url | http://hdl.handle.net/1721.1/110608 https://orcid.org/0000-0002-3526-3797 https://orcid.org/0000-0002-7609-4205 |
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