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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...

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Autores principales: Zúñiga, José, Bastida, Adolfo, Requena, Alberto, Cerezo, Javier
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
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.
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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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