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Ab Initio Partition Functions and Thermodynamic Quantities for the Molecular Hydrogen Isotopologues
[Image: see text] In this work, we calculate the partition functions and thermodynamic quantities of molecular hydrogen isotopologues using the rovibrational energy levels provided by the highly accurate ab initio adiabatic potential energy functions recently determined by Pachucki and Komasa (Pachu...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8543445/ https://www.ncbi.nlm.nih.gov/pubmed/34613734 http://dx.doi.org/10.1021/acs.jpca.1c06468 |
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author | Zúñiga, José Bastida, Adolfo Requena, Alberto Cerezo, Javier |
author_facet | Zúñiga, José Bastida, Adolfo Requena, Alberto Cerezo, Javier |
author_sort | Zúñiga, José |
collection | PubMed |
description | [Image: see text] In this work, we calculate the partition functions and thermodynamic quantities of molecular hydrogen isotopologues using the rovibrational energy levels provided by the highly accurate ab initio adiabatic potential energy functions recently determined by Pachucki and Komasa (Pachucki, K.; Komasa, J. J. Chem. Phys.2014, 141, 224103). The partition functions are calculated by including all bound energy levels of the isotopologues, up to their dissociation limits, plus the quasi-bound levels lying below the centrifugal potential barriers. For the homonuclear isotopologues, H(2), D(2), and T(2), we also determine the partition functions and thermodynamic quantities of the normal mixtures using the statistical treatment recently proposed by Colonna et al. (Colonna, G.; D’Angola, A.; Capitelli, M. Int. J. Hydrogen Energy2012, 37, 9656) based on the definition of the partition function of the mixture, which avoids inconsistencies in the values of the thermodynamic quantities depending directly on the internal partition function, in the high-temperature limit. |
format | Online Article Text |
id | pubmed-8543445 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-85434452021-10-26 Ab Initio Partition Functions and Thermodynamic Quantities for the Molecular Hydrogen Isotopologues Zúñiga, José Bastida, Adolfo Requena, Alberto Cerezo, Javier J Phys Chem A [Image: see text] In this work, we calculate the partition functions and thermodynamic quantities of molecular hydrogen isotopologues using the rovibrational energy levels provided by the highly accurate ab initio adiabatic potential energy functions recently determined by Pachucki and Komasa (Pachucki, K.; Komasa, J. J. Chem. Phys.2014, 141, 224103). The partition functions are calculated by including all bound energy levels of the isotopologues, up to their dissociation limits, plus the quasi-bound levels lying below the centrifugal potential barriers. For the homonuclear isotopologues, H(2), D(2), and T(2), we also determine the partition functions and thermodynamic quantities of the normal mixtures using the statistical treatment recently proposed by Colonna et al. (Colonna, G.; D’Angola, A.; Capitelli, M. Int. J. Hydrogen Energy2012, 37, 9656) based on the definition of the partition function of the mixture, which avoids inconsistencies in the values of the thermodynamic quantities depending directly on the internal partition function, in the high-temperature limit. American Chemical Society 2021-10-06 2021-10-21 /pmc/articles/PMC8543445/ /pubmed/34613734 http://dx.doi.org/10.1021/acs.jpca.1c06468 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Zúñiga, José Bastida, Adolfo Requena, Alberto Cerezo, Javier Ab Initio Partition Functions and Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title | Ab Initio Partition Functions and
Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title_full | Ab Initio Partition Functions and
Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title_fullStr | Ab Initio Partition Functions and
Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title_full_unstemmed | Ab Initio Partition Functions and
Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title_short | Ab Initio Partition Functions and
Thermodynamic Quantities for the Molecular Hydrogen Isotopologues |
title_sort | ab initio partition functions and
thermodynamic quantities for the molecular hydrogen isotopologues |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8543445/ https://www.ncbi.nlm.nih.gov/pubmed/34613734 http://dx.doi.org/10.1021/acs.jpca.1c06468 |
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