dorsal/arxiv
View SchemaAb initio thermochemistry beyond chemical accuracy for first-and second-row compounds
| Authors | Jan M. L. Martin |
|---|---|
| Categories | |
| ArXiv ID | physics/9808013 |
| URL | https://arxiv.org/abs/physics/9808013 |
| Journal | NATO ASI Series C 535, 373-415 (1999) [ISBN 0-7923-5741-8] |
Abstract
By judicious use of extrapolations to the 1-particle basis set limit and $n$-particle calibration techniques, total atomization energies of molecules with up to four heavy atoms can be obtained with calibration accuracy (1 kJ/mol or better, on average) without any empirical correction. For the SCF energy a 3-point geometric extrapolation is the method of choice. For the MP2 correlation energy, a 2-point $A+B/(l+1/2)^3$ extrapolation is recommended, while for CCSD and CCSD(T) correlation energies we prefer the 3-point $A+B/(l+1/2)^C$ formula. Addition of high-exponent `inner polarization functions' to second-row atoms is essential for reliable results. For the highest accuracy, accounts are required of inner-shell correlation, atomic spin-orbit splitting, anharmonicity in the zero-point energy, and scalar relativistic effects.
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"abstract": "By judicious use of extrapolations to the 1-particle basis set limit and\n$n$-particle calibration techniques, total atomization energies of molecules\nwith up to four heavy atoms can be obtained with calibration accuracy (1 kJ/mol\nor better, on average) without any empirical correction. For the SCF energy a\n3-point geometric extrapolation is the method of choice. For the MP2\ncorrelation energy, a 2-point $A+B/(l+1/2)^3$ extrapolation is recommended,\nwhile for CCSD and CCSD(T) correlation energies we prefer the 3-point\n$A+B/(l+1/2)^C$ formula. Addition of high-exponent `inner polarization\nfunctions\u0027 to second-row atoms is essential for reliable results. For the\nhighest accuracy, accounts are required of inner-shell correlation, atomic\nspin-orbit splitting, anharmonicity in the zero-point energy, and scalar\nrelativistic effects.",
"arxiv_id": "physics/9808013",
"authors": [
"Jan M. L. Martin"
],
"categories": [
"physics.chem-ph"
],
"journal_ref": "NATO ASI Series C 535, 373-415 (1999) [ISBN 0-7923-5741-8]",
"title": "Ab initio thermochemistry beyond chemical accuracy for first-and second-row compounds",
"url": "https://arxiv.org/abs/physics/9808013"
},
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