A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet
<p>Accurate reference spectroscopic information for the water molecule from the microwave to the near-ultraviolet is of paramount importance in atmospheric research. A semi-empirical potential energy surface for the ground electronic state of <span class="inline-formula"><ma...
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| Format: | Article |
| Language: | English |
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Copernicus Publications
2020-08-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://acp.copernicus.org/articles/20/10015/2020/acp-20-10015-2020.pdf |
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| author | E. K. Conway E. K. Conway I. E. Gordon J. Tennyson O. L. Polyansky S. N. Yurchenko K. Chance |
| author_facet | E. K. Conway E. K. Conway I. E. Gordon J. Tennyson O. L. Polyansky S. N. Yurchenko K. Chance |
| author_sort | E. K. Conway |
| collection | DOAJ |
| description | <p>Accurate reference spectroscopic information for the water molecule from the microwave to the near-ultraviolet is of paramount importance in atmospheric research. A semi-empirical potential energy surface for the ground electronic state of <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow class="chem"><msubsup><mi mathvariant="normal">H</mi><mn mathvariant="normal">2</mn><mn mathvariant="normal">16</mn></msubsup><mi mathvariant="normal">O</mi></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="28pt" height="17pt" class="svg-formula" dspmath="mathimg" md5hash="11c6760be345254f33f3f3e4de36fc5b"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-20-10015-2020-ie00004.svg" width="28pt" height="17pt" src="acp-20-10015-2020-ie00004.png"/></svg:svg></span></span> has been created by refining almost 4000 experimentally determined energy levels. These states extend into regions with large values of rotational and vibrational excitation. For all states considered in our refinement procedure, which extend to 37 000 cm<span class="inline-formula"><sup>−1</sup></span> and <span class="inline-formula"><i>J</i>=20</span> (total angular momentum), the average root-mean-square deviation is approximately 0.05 cm<span class="inline-formula"><sup>−1</sup></span>. This potential energy surface offers significant improvements when compared to recent models by accurately predicting states possessing high values of <span class="inline-formula"><i>J</i></span>. This feature will offer significant improvements in calculated line positions for high-temperature spectra where transitions between high <span class="inline-formula"><i>J</i></span> states become more prominent.</p>
<p>Combining this potential with the latest dipole moment surface for water vapour, a line list has been calculated which extends reliably to 37 000 cm<span class="inline-formula"><sup>−1</sup></span>. Obtaining reliable results in the ultraviolet is of special importance as it is a challenging spectral region for the water molecule both experimentally and theoretically. Comparisons are made against several experimental sources of cross sections in the near-ultraviolet and discrepancies are observed. In the near-ultraviolet our calculations are in agreement with recent atmospheric retrievals and the upper limit obtained using broadband spectroscopy by <span class="cit" id="xref_text.1"><a href="#bib1.bibx69">Wilson et al.</a> (<a href="#bib1.bibx69">2016</a>, p. 194)</span>, but they do not support recent suggestions of very strong absorption in this region.</p> |
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| issn | 1680-7316 1680-7324 |
| language | English |
| last_indexed | 2024-12-13T09:11:43Z |
| publishDate | 2020-08-01 |
| publisher | Copernicus Publications |
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| series | Atmospheric Chemistry and Physics |
| spelling | doaj.art-91c7637f784744c7892b32c361332c7a2022-12-21T23:52:54ZengCopernicus PublicationsAtmospheric Chemistry and Physics1680-73161680-73242020-08-0120100151002710.5194/acp-20-10015-2020A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultravioletE. K. Conway0E. K. Conway1I. E. Gordon2J. Tennyson3O. L. Polyansky4S. N. Yurchenko5K. Chance6Center for Astrophysics, Harvard and Smithsonian, Atomic and Molecular Physics Division, Cambridge, MA 02138, USADepartment of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UKCenter for Astrophysics, Harvard and Smithsonian, Atomic and Molecular Physics Division, Cambridge, MA 02138, USADepartment of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UKDepartment of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UKDepartment of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, UKCenter for Astrophysics, Harvard and Smithsonian, Atomic and Molecular Physics Division, Cambridge, MA 02138, USA<p>Accurate reference spectroscopic information for the water molecule from the microwave to the near-ultraviolet is of paramount importance in atmospheric research. A semi-empirical potential energy surface for the ground electronic state of <span class="inline-formula"><math xmlns="http://www.w3.org/1998/Math/MathML" id="M3" display="inline" overflow="scroll" dspmath="mathml"><mrow class="chem"><msubsup><mi mathvariant="normal">H</mi><mn mathvariant="normal">2</mn><mn mathvariant="normal">16</mn></msubsup><mi mathvariant="normal">O</mi></mrow></math><span><svg:svg xmlns:svg="http://www.w3.org/2000/svg" width="28pt" height="17pt" class="svg-formula" dspmath="mathimg" md5hash="11c6760be345254f33f3f3e4de36fc5b"><svg:image xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="acp-20-10015-2020-ie00004.svg" width="28pt" height="17pt" src="acp-20-10015-2020-ie00004.png"/></svg:svg></span></span> has been created by refining almost 4000 experimentally determined energy levels. These states extend into regions with large values of rotational and vibrational excitation. For all states considered in our refinement procedure, which extend to 37 000 cm<span class="inline-formula"><sup>−1</sup></span> and <span class="inline-formula"><i>J</i>=20</span> (total angular momentum), the average root-mean-square deviation is approximately 0.05 cm<span class="inline-formula"><sup>−1</sup></span>. This potential energy surface offers significant improvements when compared to recent models by accurately predicting states possessing high values of <span class="inline-formula"><i>J</i></span>. This feature will offer significant improvements in calculated line positions for high-temperature spectra where transitions between high <span class="inline-formula"><i>J</i></span> states become more prominent.</p> <p>Combining this potential with the latest dipole moment surface for water vapour, a line list has been calculated which extends reliably to 37 000 cm<span class="inline-formula"><sup>−1</sup></span>. Obtaining reliable results in the ultraviolet is of special importance as it is a challenging spectral region for the water molecule both experimentally and theoretically. Comparisons are made against several experimental sources of cross sections in the near-ultraviolet and discrepancies are observed. In the near-ultraviolet our calculations are in agreement with recent atmospheric retrievals and the upper limit obtained using broadband spectroscopy by <span class="cit" id="xref_text.1"><a href="#bib1.bibx69">Wilson et al.</a> (<a href="#bib1.bibx69">2016</a>, p. 194)</span>, but they do not support recent suggestions of very strong absorption in this region.</p>https://acp.copernicus.org/articles/20/10015/2020/acp-20-10015-2020.pdf |
| spellingShingle | E. K. Conway E. K. Conway I. E. Gordon J. Tennyson O. L. Polyansky S. N. Yurchenko K. Chance A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet Atmospheric Chemistry and Physics |
| title | A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet |
| title_full | A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet |
| title_fullStr | A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet |
| title_full_unstemmed | A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet |
| title_short | A semi-empirical potential energy surface and line list for H<sub>2</sub><sup>16</sup>O extending into the near-ultraviolet |
| title_sort | semi empirical potential energy surface and line list for h sub 2 sub sup 16 sup o extending into the near ultraviolet |
| url | https://acp.copernicus.org/articles/20/10015/2020/acp-20-10015-2020.pdf |
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