Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements.
Despite being one of the best-known families of organic compounds, the fact that hydrocarbons exhibit a rich variety of structures owing to branching, cyclization, and the presence of multiple bonds, means that many of their properties are yet to be determined accurately, or even at all. Among cycli...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-12-01
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| Series: | Chemical Thermodynamics and Thermal Analysis |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667312623000184 |
| _version_ | 1797398394084261888 |
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| author | Zoi Salta Nicola Tasinato Joel F. Liebman Oscar N. Ventura |
| author_facet | Zoi Salta Nicola Tasinato Joel F. Liebman Oscar N. Ventura |
| author_sort | Zoi Salta |
| collection | DOAJ |
| description | Despite being one of the best-known families of organic compounds, the fact that hydrocarbons exhibit a rich variety of structures owing to branching, cyclization, and the presence of multiple bonds, means that many of their properties are yet to be determined accurately, or even at all. Among cyclic hydrocarbons, those with three-membered rings are particularly interesting because of their strain energy. In this paper, we report accurate calculations of the enthalpy of formation of three-membered carbocycles, whose experimental values have not been obtained by direct measurement of the heat of combustion. For this purpose, we used several accurate composite methods to obtain the gas-phase enthalpies of atomization and derived from them the gas-phase enthalpies of formation, using experimentally determined accurate values for the atoms. Moreover, to minimize the inaccuracy that can possibly arise in this procedure, we also used homodesmotic reactions designed to balance systematic errors in the geometric and electronic structure of some of the species. A careful analysis of the results shows that some of the indirectly derived values reported in the literature are far from the most accurate theoretical outcomes, and we suggest that these new ones should be adopted. |
| first_indexed | 2024-03-09T01:25:01Z |
| format | Article |
| id | doaj.art-07b171a199d64859b988464be29e7640 |
| institution | Directory Open Access Journal |
| issn | 2667-3126 |
| language | English |
| last_indexed | 2024-03-09T01:25:01Z |
| publishDate | 2023-12-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Chemical Thermodynamics and Thermal Analysis |
| spelling | doaj.art-07b171a199d64859b988464be29e76402023-12-10T06:18:59ZengElsevierChemical Thermodynamics and Thermal Analysis2667-31262023-12-0112100121Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements.Zoi Salta0Nicola Tasinato1Joel F. Liebman2Oscar N. Ventura3Scuola Normale Superiore, Piazza dei Cavalieri 7, Pisa 56126, Italy; Corresponding author at: Scuola Normale Superiore, Piazza dei Cavalieri 7, Pisa 56126, Italy.Scuola Normale Superiore, Piazza dei Cavalieri 7, Pisa 56126, ItalyDepartment of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD, USAComputational Chemistry and Biology Group, Detema, School of Chemistry, UdelaR, Uruguay; Corresponding author at: Computational Chemistry and Biology Group, Detema, Facultad de Química, Universidad de la República, Isidoro de María 1610, 2100 Montevideo, Uruguay.Despite being one of the best-known families of organic compounds, the fact that hydrocarbons exhibit a rich variety of structures owing to branching, cyclization, and the presence of multiple bonds, means that many of their properties are yet to be determined accurately, or even at all. Among cyclic hydrocarbons, those with three-membered rings are particularly interesting because of their strain energy. In this paper, we report accurate calculations of the enthalpy of formation of three-membered carbocycles, whose experimental values have not been obtained by direct measurement of the heat of combustion. For this purpose, we used several accurate composite methods to obtain the gas-phase enthalpies of atomization and derived from them the gas-phase enthalpies of formation, using experimentally determined accurate values for the atoms. Moreover, to minimize the inaccuracy that can possibly arise in this procedure, we also used homodesmotic reactions designed to balance systematic errors in the geometric and electronic structure of some of the species. A careful analysis of the results shows that some of the indirectly derived values reported in the literature are far from the most accurate theoretical outcomes, and we suggest that these new ones should be adopted.http://www.sciencedirect.com/science/article/pii/S2667312623000184carbocyclesenthalpy of formationstrain energycomposite methods |
| spellingShingle | Zoi Salta Nicola Tasinato Joel F. Liebman Oscar N. Ventura Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. Chemical Thermodynamics and Thermal Analysis carbocycles enthalpy of formation strain energy composite methods |
| title | Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. |
| title_full | Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. |
| title_fullStr | Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. |
| title_full_unstemmed | Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. |
| title_short | Enthalpy of Formation of Carbocycles: A Precise Theoretical Determination of Experimentally Imprecise Measurements. |
| title_sort | enthalpy of formation of carbocycles a precise theoretical determination of experimentally imprecise measurements |
| topic | carbocycles enthalpy of formation strain energy composite methods |
| url | http://www.sciencedirect.com/science/article/pii/S2667312623000184 |
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