dorsal/arxiv
View SchemaThe heats of formation of the haloacetylenes XCCY [X, Y = H, F, Cl]: basis set limit ab initio results and thermochemical analysis
| Authors | Srinivasan Parthiban, Jan M. L. Martin, Joel F. Liebman |
|---|---|
| Categories | |
| ArXiv ID | physics/0108036 |
| URL | https://arxiv.org/abs/physics/0108036 |
| DOI | 10.1080/00268970110082015 |
Abstract
The heats of formation of haloacetylenes are evaluated using the recent W1 and W2 ab initio computational thermochemistry methods. These calculations involve CCSD and CCSD(T) coupled cluster methods, basis sets of up to spdfgh quality, extrapolations to the one-particle basis set limit, and contributions of inner-shell correlation, scalar relativistic effects, and (where relevant) first-order spin-orbit coupling. The heats of formation determined using W2 theory are: \hof(HCCH) = 54.48 kcal/mol, \hof(HCCF) = 25.15 kcal/mol, \hof(FCCF) = 1.38 kcal/mol, \hof(HCCCl) = 54.83 kcal/mol, \hof(ClCCCl) = 56.21 kcal/mol, and \hof(FCCCl) = 28.47 kcal/mol. Enthalpies of hydrogenation and destabilization energies relative to acetylene were obtained at the W1 level of theory. So doing we find the following destabilization order for acetylenes: FCCF $>$ ClCCF $>$ HCCF $>$ ClCCCl $>$ HCCCl $>$ HCCH. By a combination of W1 theory and isodesmic reactions, we show that the generally accepted heat of formation of 1,2-dichloroethane should be revised to -31.8$\pm$0.6 kcal/mol, in excellent agreement with a very recent critically evaluated review. The performance of compound thermochemistry schemes such as G2, G3, G3X and CBS-QB3 theories has been analyzed.
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"abstract": "The heats of formation of haloacetylenes are evaluated using the recent W1\nand W2 ab initio computational thermochemistry methods. These calculations\ninvolve CCSD and CCSD(T) coupled cluster methods, basis sets of up to spdfgh\nquality, extrapolations to the one-particle basis set limit, and contributions\nof inner-shell correlation, scalar relativistic effects, and (where relevant)\nfirst-order spin-orbit coupling. The heats of formation determined using W2\ntheory are: \\hof(HCCH) = 54.48 kcal/mol, \\hof(HCCF) = 25.15 kcal/mol,\n\\hof(FCCF) = 1.38 kcal/mol, \\hof(HCCCl) = 54.83 kcal/mol, \\hof(ClCCCl) = 56.21\nkcal/mol, and \\hof(FCCCl) = 28.47 kcal/mol. Enthalpies of hydrogenation and\ndestabilization energies relative to acetylene were obtained at the W1 level of\ntheory. So doing we find the following destabilization order for acetylenes:\nFCCF $\u003e$ ClCCF $\u003e$ HCCF $\u003e$ ClCCCl $\u003e$ HCCCl $\u003e$ HCCH. By a combination of W1\ntheory and isodesmic reactions, we show that the generally accepted heat of\nformation of 1,2-dichloroethane should be revised to -31.8$\\pm$0.6 kcal/mol, in\nexcellent agreement with a very recent critically evaluated review. The\nperformance of compound thermochemistry schemes such as G2, G3, G3X and CBS-QB3\ntheories has been analyzed.",
"arxiv_id": "physics/0108036",
"authors": [
"Srinivasan Parthiban",
"Jan M. L. Martin",
"Joel F. Liebman"
],
"categories": [
"physics.chem-ph",
"physics.ao-ph"
],
"doi": "10.1080/00268970110082015",
"title": "The heats of formation of the haloacetylenes XCCY [X, Y = H, F, Cl]: basis set limit ab initio results and thermochemical analysis",
"url": "https://arxiv.org/abs/physics/0108036"
},
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