dorsal/arxiv
View SchemaA definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4
| Authors | Jan M. L. Martin, Peter R. Taylor |
|---|---|
| Categories | |
| ArXiv ID | physics/9902054 |
| URL | https://arxiv.org/abs/physics/9902054 |
| DOI | 10.1021/jp9904466 |
| Journal | J. Phys. Chem. A 103, 4427-4431 (1999) |
Abstract
In order to resolve a significant uncertainty in the heat of vaporization of silicon -- a fundamental parameter in gas-phase thermochemistry -- $\Delta H^\circ_{f,0}$[Si(g)] has been determined from a thermochemical cycle involving the precisely known experimental heats of formation of SiF_4(g) and F(g) and a benchmark calculation of the total atomization energy (TAE_0) of SiF_4 using coupled-cluster methods. Basis sets up to $[8s7p6d4f2g1h]$ on Si and $[7s6p5d4f3g2h]$ on F have been employed, and extrapolations for residual basis set incompleteness applied. The contributions of inner-shell correlation (-0.08 kcal/mol), scalar relativistic effects (-1.88 kcal/mol), atomic spin-orbit splitting (-1.97 kcal/mol), and anharmonicity in the zero-point energy (+0.04 kcal/mol) have all been explicitly accounted for. Our benchmark TAE_0=565.89 \pm 0.22 kcal/mol leads to $\Delta H^\circ_{f,0}$[Si(g)]=107.15 \pm 0.38 kcal/mol ($\Delta H^\circ_{f,298}$[Si(g)]=108.19 \pm 0.38 kcal/mol): between the JANAF/CODATA value of 106.5 \pm 1.9 kcal/mol and the revised value proposed by Grev and Schaefer [J. Chem. Phys. 97, 8389 (1992}], 108.1 \pm 0.5 kcal/mol. The revision will be relevant for future computational studies on heats of formation of silicon compounds.
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"abstract": "In order to resolve a significant uncertainty in the heat of vaporization of\nsilicon -- a fundamental parameter in gas-phase thermochemistry -- $\\Delta\nH^\\circ_{f,0}$[Si(g)] has been determined from a thermochemical cycle involving\nthe precisely known experimental heats of formation of SiF_4(g) and F(g) and a\nbenchmark calculation of the total atomization energy (TAE_0) of SiF_4 using\ncoupled-cluster methods. Basis sets up to $[8s7p6d4f2g1h]$ on Si and\n$[7s6p5d4f3g2h]$ on F have been employed, and extrapolations for residual basis\nset incompleteness applied. The contributions of inner-shell correlation (-0.08\nkcal/mol), scalar relativistic effects (-1.88 kcal/mol), atomic spin-orbit\nsplitting (-1.97 kcal/mol), and anharmonicity in the zero-point energy (+0.04\nkcal/mol) have all been explicitly accounted for. Our benchmark TAE_0=565.89\n\\pm 0.22 kcal/mol leads to $\\Delta H^\\circ_{f,0}$[Si(g)]=107.15 \\pm 0.38\nkcal/mol ($\\Delta H^\\circ_{f,298}$[Si(g)]=108.19 \\pm 0.38 kcal/mol): between\nthe JANAF/CODATA value of 106.5 \\pm 1.9 kcal/mol and the revised value proposed\nby Grev and Schaefer [J. Chem. Phys. 97, 8389 (1992}], 108.1 \\pm 0.5 kcal/mol.\nThe revision will be relevant for future computational studies on heats of\nformation of silicon compounds.",
"arxiv_id": "physics/9902054",
"authors": [
"Jan M. L. Martin",
"Peter R. Taylor"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1021/jp9904466",
"journal_ref": "J. Phys. Chem. A 103, 4427-4431 (1999)",
"title": "A definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4",
"url": "https://arxiv.org/abs/physics/9902054"
},
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