Theoretical C-H Bond Dissociation Enthalpies for CH3Br and CH2ClBr

J. Espinosa-García, S. Dóbé

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The enthalpies of formation for the closed-shell molecules CH3Br and CH2ClBr, and the free radicals CH2Br and CHClBr were estimated by ab initio molecular orbital computations using hydrogenation and isodesmic reactions as working chemical reactions. Four variants of theoretical approaches (levels) and three extended basis sets were applied in the calculations. The methods included fourth-order Møller-Plesset perturbation theory (level I), coupled-cluster theory (level II), density functional theory (level III), and Gaussian-2 (G2) theory (level IV). The standard enthalpies of formation values obtained at levels I-IV for both the closed- shell and open-shell species agreed within ±1 kcal mol-1 irrespective of the working chemical reactions chosen. No basis set effects were observed. These invariances support the reliability of the computed data and are, for the most part, due to the cancellation of the computational errors as a result of the application of the working chemical reactions where the ab initio energies are combined with established experimental enthalpies of formation. The four methods provided enthalpies of formation values for CH3Br, CH2ClBr, and CH2Br in good agreement with experimental values as well; the calculations supplied the first known enthalpy data for the CHClBr radical. The recommended standard enthalpies of formation (at 298.15 K and 1.00 atm) are the unweighted averages of the results obtained at levels I-IV with the different hydrogenation and isodesmic reactions: CH3Br, -8.9 ± 0.8; CH2ClBr, -11.5 ± 1.1; CH2Br, 40.7 ± 1.1; CHClBr, 35.1 ± 1.5 kcal mol-1. The error limits designate the estimated maximal uncertainties. These enthalpies of formation values correspond to bond dissociation enthalpies of DH° 298(BrH2C-H) = 101.7 ± 1.4 kcal mol-1 and DH° 298(BrClHC-H) = 98.7 ± 1.9 kcal mol-1.

Original languageEnglish
Pages (from-to)6387-6393
Number of pages7
JournalJournal of Physical Chemistry A
Volume103
Issue number32
Publication statusPublished - 1999

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Enthalpy
enthalpy
dissociation
Chemical reactions
chemical reactions
Hydrogenation
hydrogenation
Molecular orbitals
Invariance
cancellation
free radicals
Free Radicals
Density functional theory
invariance
molecular orbitals
perturbation theory
density functional theory
Molecules
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Theoretical C-H Bond Dissociation Enthalpies for CH3Br and CH2ClBr. / Espinosa-García, J.; Dóbé, S.

In: Journal of Physical Chemistry A, Vol. 103, No. 32, 1999, p. 6387-6393.

Research output: Contribution to journalArticle

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title = "Theoretical C-H Bond Dissociation Enthalpies for CH3Br and CH2ClBr",
abstract = "The enthalpies of formation for the closed-shell molecules CH3Br and CH2ClBr, and the free radicals CH2Br and CHClBr were estimated by ab initio molecular orbital computations using hydrogenation and isodesmic reactions as working chemical reactions. Four variants of theoretical approaches (levels) and three extended basis sets were applied in the calculations. The methods included fourth-order M{\o}ller-Plesset perturbation theory (level I), coupled-cluster theory (level II), density functional theory (level III), and Gaussian-2 (G2) theory (level IV). The standard enthalpies of formation values obtained at levels I-IV for both the closed- shell and open-shell species agreed within ±1 kcal mol-1 irrespective of the working chemical reactions chosen. No basis set effects were observed. These invariances support the reliability of the computed data and are, for the most part, due to the cancellation of the computational errors as a result of the application of the working chemical reactions where the ab initio energies are combined with established experimental enthalpies of formation. The four methods provided enthalpies of formation values for CH3Br, CH2ClBr, and CH2Br in good agreement with experimental values as well; the calculations supplied the first known enthalpy data for the CHClBr radical. The recommended standard enthalpies of formation (at 298.15 K and 1.00 atm) are the unweighted averages of the results obtained at levels I-IV with the different hydrogenation and isodesmic reactions: CH3Br, -8.9 ± 0.8; CH2ClBr, -11.5 ± 1.1; CH2Br, 40.7 ± 1.1; CHClBr, 35.1 ± 1.5 kcal mol-1. The error limits designate the estimated maximal uncertainties. These enthalpies of formation values correspond to bond dissociation enthalpies of DH° 298(BrH2C-H) = 101.7 ± 1.4 kcal mol-1 and DH° 298(BrClHC-H) = 98.7 ± 1.9 kcal mol-1.",
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