Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species
This work reports a detailed theoretical study of the molecular parameters, harmonic vibrational frequencies, UV absorption spectra and standard enthalpies of formation for the radicals C2X3 (with X = F, Cl and Br) and a comparison with the corresponding determinations for the rest of the members of...
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The Royal Society
2024-11-01
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| Online Access: | https://royalsocietypublishing.org/doi/10.1098/rsos.240448 |
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| author | María Liz Ferreira Franco Ignacio Dubois María Eugenia Tucceri María Paula Badenes |
| author_facet | María Liz Ferreira Franco Ignacio Dubois María Eugenia Tucceri María Paula Badenes |
| author_sort | María Liz Ferreira |
| collection | DOAJ |
| description | This work reports a detailed theoretical study of the molecular parameters, harmonic vibrational frequencies, UV absorption spectra and standard enthalpies of formation for the radicals C2X3 (with X = F, Cl and Br) and a comparison with the corresponding determinations for the rest of the members of the family C2Xn (with n = 2-4). Molecular properties were calculated using different levels of theory: density functional theory employing the B3LYP, X3LYP, BMK, M06-2X and M08-HX functionals combined with the basis sets 6–311++G(3df,3pd) and aug-cc-pVTZ, and the ab initio composite models G3B3 and G4. Structural and spectroscopic characterization of the C2F3, C2Cl3 and C2Br3 radicals, along with the estimation of the enthalpies of formation of C2F3 and C2Cl3, were derived here for the first time, to our knowledge. In particular, values of −220.9 ± 2.9, 230.8 ± 3.8 and 375.4 ± 5.9 kJ mol−1 were computed for enthalpies of formation of C2F3, C2Cl3 and C2Br3, respectively. Additionally, enthalpies of formation for related closed-shell molecules were obtained with less uncertainty compared to those found in the literature. The recommended values of −669.6 ± 3.8, −23.0 ± 4.6 and 155.3 ± 5.0 kJ mol−1 were derived for C2F4, C2Cl4 and C2Br4, while corresponding values of 0.6 ± 6.3, 228.1 ± 2.1 and 319.6 ± 5.4 kJ mol−1 were estimated for C2F2, C2Cl2 and C2Br2, respectively. |
| format | Article |
| id | doaj-art-423d71e294f34d088b8967a986eab170 |
| institution | Kabale University |
| issn | 2054-5703 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | The Royal Society |
| record_format | Article |
| series | Royal Society Open Science |
| spelling | doaj-art-423d71e294f34d088b8967a986eab1702024-11-20T00:05:19ZengThe Royal SocietyRoyal Society Open Science2054-57032024-11-01111110.1098/rsos.240448Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related speciesMaría Liz Ferreira0Franco Ignacio Dubois1María Eugenia Tucceri2María Paula Badenes3Facultad de Ciencias Exactas, Departamento de Química, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CCT La Plata-CONICET, Casilla de Correo 16, Sucursal 4, (1900), La Plata, ArgentinaFacultad de Ciencias Exactas, Departamento de Química, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CCT La Plata-CONICET, Casilla de Correo 16, Sucursal 4, (1900), La Plata, ArgentinaFacultad de Ciencias Exactas, Departamento de Química, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CCT La Plata-CONICET, Casilla de Correo 16, Sucursal 4, (1900), La Plata, ArgentinaFacultad de Ciencias Exactas, Departamento de Química, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Universidad Nacional de La Plata, CCT La Plata-CONICET, Casilla de Correo 16, Sucursal 4, (1900), La Plata, ArgentinaThis work reports a detailed theoretical study of the molecular parameters, harmonic vibrational frequencies, UV absorption spectra and standard enthalpies of formation for the radicals C2X3 (with X = F, Cl and Br) and a comparison with the corresponding determinations for the rest of the members of the family C2Xn (with n = 2-4). Molecular properties were calculated using different levels of theory: density functional theory employing the B3LYP, X3LYP, BMK, M06-2X and M08-HX functionals combined with the basis sets 6–311++G(3df,3pd) and aug-cc-pVTZ, and the ab initio composite models G3B3 and G4. Structural and spectroscopic characterization of the C2F3, C2Cl3 and C2Br3 radicals, along with the estimation of the enthalpies of formation of C2F3 and C2Cl3, were derived here for the first time, to our knowledge. In particular, values of −220.9 ± 2.9, 230.8 ± 3.8 and 375.4 ± 5.9 kJ mol−1 were computed for enthalpies of formation of C2F3, C2Cl3 and C2Br3, respectively. Additionally, enthalpies of formation for related closed-shell molecules were obtained with less uncertainty compared to those found in the literature. The recommended values of −669.6 ± 3.8, −23.0 ± 4.6 and 155.3 ± 5.0 kJ mol−1 were derived for C2F4, C2Cl4 and C2Br4, while corresponding values of 0.6 ± 6.3, 228.1 ± 2.1 and 319.6 ± 5.4 kJ mol−1 were estimated for C2F2, C2Cl2 and C2Br2, respectively.https://royalsocietypublishing.org/doi/10.1098/rsos.240448quantum-chemical calculationsstandard enthalpy of formationUV absorption spectratrifluoroethenyl radicaltrichloroethenyl radicaltribromoethenyl radical |
| spellingShingle | María Liz Ferreira Franco Ignacio Dubois María Eugenia Tucceri María Paula Badenes Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species Royal Society Open Science quantum-chemical calculations standard enthalpy of formation UV absorption spectra trifluoroethenyl radical trichloroethenyl radical tribromoethenyl radical |
| title | Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species |
| title_full | Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species |
| title_fullStr | Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species |
| title_full_unstemmed | Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species |
| title_short | Molecular, spectroscopic and thermochemical characterization of C2Cl3, C2F3 and C2Br3 radicals and related species |
| title_sort | molecular spectroscopic and thermochemical characterization of c2cl3 c2f3 and c2br3 radicals and related species |
| topic | quantum-chemical calculations standard enthalpy of formation UV absorption spectra trifluoroethenyl radical trichloroethenyl radical tribromoethenyl radical |
| url | https://royalsocietypublishing.org/doi/10.1098/rsos.240448 |
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