Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule
We calculate harmonic frequencies of the three most abundant carbonic acid conformers. For this, different model chemistries are investigated with respect to their benefits and shortcomings. Based on these results we use perturbation theory to calculate anharmonic corrections at the ωB97XD/aug-cc-pV...
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craippubl:10.1063/1.4755786 2024-06-23T07:52:02+00:00 Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule Huber, Stefan E. Dalnodar, Silvia Kausch, Wolfgang Kimeswenger, Stefan Probst, Michael 2012 http://dx.doi.org/10.1063/1.4755786 https://pubs.aip.org/aip/adv/article-pdf/doi/10.1063/1.4755786/12953402/032180_1_online.pdf en eng AIP Publishing AIP Advances volume 2, issue 3 ISSN 2158-3226 journal-article 2012 craippubl https://doi.org/10.1063/1.4755786 2024-05-30T08:08:10Z We calculate harmonic frequencies of the three most abundant carbonic acid conformers. For this, different model chemistries are investigated with respect to their benefits and shortcomings. Based on these results we use perturbation theory to calculate anharmonic corrections at the ωB97XD/aug-cc-pVXZ, X = D, T, Q, level of theory and compare them with recent experimental data and theoretical predictions. A discrete variable representation method is used to predict the large anharmonic contributions to the frequencies of the stretching vibrations in the hydrogen bonds in the carbonic acid dimer. Moreover, we re-investigate the energetics of the formation of the carbonic acid dimer from its constituents water and carbon dioxide using a high-level extrapolation method. We find that the ωB97XD functional performs well in estimating the fundamental frequencies of the carbonic acid conformers. Concerning the reaction energetics, the accuracy of ωB97XD is even comparable to the high-level extrapolation method. We discuss possibilities to detect carbonic acid in various natural environments such as Earth's and Martian atmospheres. Article in Journal/Newspaper Carbonic acid AIP Publishing AIP Advances 2 3 032180 |
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Open Polar |
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AIP Publishing |
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craippubl |
language |
English |
description |
We calculate harmonic frequencies of the three most abundant carbonic acid conformers. For this, different model chemistries are investigated with respect to their benefits and shortcomings. Based on these results we use perturbation theory to calculate anharmonic corrections at the ωB97XD/aug-cc-pVXZ, X = D, T, Q, level of theory and compare them with recent experimental data and theoretical predictions. A discrete variable representation method is used to predict the large anharmonic contributions to the frequencies of the stretching vibrations in the hydrogen bonds in the carbonic acid dimer. Moreover, we re-investigate the energetics of the formation of the carbonic acid dimer from its constituents water and carbon dioxide using a high-level extrapolation method. We find that the ωB97XD functional performs well in estimating the fundamental frequencies of the carbonic acid conformers. Concerning the reaction energetics, the accuracy of ωB97XD is even comparable to the high-level extrapolation method. We discuss possibilities to detect carbonic acid in various natural environments such as Earth's and Martian atmospheres. |
format |
Article in Journal/Newspaper |
author |
Huber, Stefan E. Dalnodar, Silvia Kausch, Wolfgang Kimeswenger, Stefan Probst, Michael |
spellingShingle |
Huber, Stefan E. Dalnodar, Silvia Kausch, Wolfgang Kimeswenger, Stefan Probst, Michael Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
author_facet |
Huber, Stefan E. Dalnodar, Silvia Kausch, Wolfgang Kimeswenger, Stefan Probst, Michael |
author_sort |
Huber, Stefan E. |
title |
Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
title_short |
Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
title_full |
Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
title_fullStr |
Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
title_full_unstemmed |
Carbonic acid revisited: Vibrational spectra, energetics and the possibility of detecting an elusive molecule |
title_sort |
carbonic acid revisited: vibrational spectra, energetics and the possibility of detecting an elusive molecule |
publisher |
AIP Publishing |
publishDate |
2012 |
url |
http://dx.doi.org/10.1063/1.4755786 https://pubs.aip.org/aip/adv/article-pdf/doi/10.1063/1.4755786/12953402/032180_1_online.pdf |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
AIP Advances volume 2, issue 3 ISSN 2158-3226 |
op_doi |
https://doi.org/10.1063/1.4755786 |
container_title |
AIP Advances |
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2 |
container_issue |
3 |
container_start_page |
032180 |
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1802643228066840576 |