Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction
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| Formato: | Artículo publishedVersion |
| Lenguaje: | Inglés |
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Elsevier
2025
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| Acceso en línea: | http://repositorio.ungs.edu.ar:8080/xmlui/handle/UNGS/2310 |
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I71-R177-UNGS-2310 |
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I71-R177-UNGS-23102025-07-11T18:00:43Z Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction Gómez, Nicolás D. Azcárate, M. Laura Codnia, Jorge Cobos, Carlos J. CCl2 HCl CHCl3 Quantum-chemical calculations Transition state theory Halogenated radicals Ciencias Físicas Revista con referato Fil: Codnia, Jorge. Universidad Nacional de General Sarmiento. Instituto de Ciencias; Argentina. Fil: Codnia, Jorge. Instituto de Investigaciones Científicas y Técnicas para la Defensa. Departamento de Investigaciones en Láseres y sus aplicaciones; Argentina. Fil: Gómez, Nicolás D. Instituto de Investigaciones Científicas y Técnicas para la Defensa. Departamento de Investigaciones en Láseres y sus aplicaciones; Argentina. Fil: Azcárate, M. Laura. Instituto de Investigaciones Científicas y Técnicas para la Defensa. Departamento de Investigaciones en Láseres y sus aplicaciones; Argentina. The CCl2 + HCl → CHCl3 (1) insertion reaction has been investigated by ab initio molecular orbital and kinetic calculations. The geometries of reactants, products and transition state were optimized with a large number of density functional theory (DFT) formulations combined with the 6-311++G(3df,3pd) basis set. The reaction barriers calculated with G4(MP2)//DFT and G4//DFT theories of 1.16 ± 0.27 and 0.61 ± 0.26 kcal mol−1 are consistent with the barrier height of ΔE0# = 1.54 ± 0.30 kcal mol−1 estimated from the room temperature experimental rate constant. Calculated enthalpies of reaction of −53.97 ± 0.09 (G4(MP2)//DFT), −55.27 ± 0.09 (G4//DFT) and −56.52 ± 3.90 kcal mol−1 (DFT) agree well with experimental values. The obtained rate constants over the 300–2000 K temperature range at the high and low pressure limit can be expressed as k1,∞(G4(MP2)//DFT) = (4.8 ± 1.8) × 10−14 (T/300 K)2.12±0.19 and k1,∞(G4//DFT) = (9.8 ± 3.4) × 10−14 (T/300 K)1.77±0.16 in cm3 molecule−1 s−1, and k1,0 = [HCl] 3.40 × 10−27 (T/300 K)−6.57 exp(−2218 K/T) cm3 molecule−1 s−1. Falloff curves for the intermediate pressure range obtained for the reactions (1, −1) with these rate constants and a derived central broadening factor of Fcent = 0.16 + 0.84 exp(−T/331 K) + exp(−7860 K/T) were compared with reported experimental rate data. 2025-07-11T17:49:08Z 2025-07-11T17:49:08Z 2020 info:eu-repo/semantics/article info:ar-repo/semantics/artículo info:eu-repo/semantics/publishedVersion Gómez, N. D., Azcárate, M. L., Codnia, J. y Cobos, C. J. (2020). Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction. Computational and Theoretical Chemistry, 1176, 112742. 2210-271X http://repositorio.ungs.edu.ar:8080/xmlui/handle/UNGS/2310 eng https://doi.org/10.1016/j.comptc.2020.112742 info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf application/pdf Elsevier Computational and Theoretical Chemistry. Abr. 2020; 1176: 112742 https://www.sciencedirect.com/journal/computational-and-theoretical-chemistry/vol/1176/suppl/C |
| institution |
Universidad Nacional de General Sarmiento |
| institution_str |
I-71 |
| repository_str |
R-177 |
| collection |
Repositorio Institucional Digital de Acceso Abierto (UNGS) |
| language |
Inglés |
| orig_language_str_mv |
eng |
| topic |
CCl2 HCl CHCl3 Quantum-chemical calculations Transition state theory Halogenated radicals Ciencias Físicas |
| spellingShingle |
CCl2 HCl CHCl3 Quantum-chemical calculations Transition state theory Halogenated radicals Ciencias Físicas Gómez, Nicolás D. Azcárate, M. Laura Codnia, Jorge Cobos, Carlos J. Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| topic_facet |
CCl2 HCl CHCl3 Quantum-chemical calculations Transition state theory Halogenated radicals Ciencias Físicas |
| description |
Revista con referato |
| format |
Artículo Artículo publishedVersion |
| author |
Gómez, Nicolás D. Azcárate, M. Laura Codnia, Jorge Cobos, Carlos J. |
| author_facet |
Gómez, Nicolás D. Azcárate, M. Laura Codnia, Jorge Cobos, Carlos J. |
| author_sort |
Gómez, Nicolás D. |
| title |
Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| title_short |
Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| title_full |
Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| title_fullStr |
Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| title_full_unstemmed |
Quantum chemical and kinetic study of the CCl2+HCl→CHCl3 insertion reaction |
| title_sort |
quantum chemical and kinetic study of the ccl2+hcl→chcl3 insertion reaction |
| publisher |
Elsevier |
| publishDate |
2025 |
| url |
http://repositorio.ungs.edu.ar:8080/xmlui/handle/UNGS/2310 |
| work_keys_str_mv |
AT gomeznicolasd quantumchemicalandkineticstudyoftheccl2hclchcl3insertionreaction AT azcaratemlaura quantumchemicalandkineticstudyoftheccl2hclchcl3insertionreaction AT codniajorge quantumchemicalandkineticstudyoftheccl2hclchcl3insertionreaction AT coboscarlosj quantumchemicalandkineticstudyoftheccl2hclchcl3insertionreaction |
| _version_ |
1842217797498699776 |