Ab initio thermochemistry beyond chemical accuracy for first-and second-row compounds

dc.creatorMartin, Jan M. L.
dc.date1998-08-12
dc.date.accessioned2026-07-07T05:56:19Z
dc.date.available2026-07-07T05:56:19Z
dc.descriptionBy 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.
dc.description43 pages, in upcoming NATO ASI volume "Energetics of stable molecules and reactive intermediates" (ed. M. E. Minas da Piedade)
dc.identifierhttps://arxiv.org/abs/physics/9808013
dc.identifierhttp://arxiv.org/abs/physics/9808013
dc.identifierNATO ASI Series C 535, 373-415 (1999) [ISBN 0-7923-5741-8]
dc.identifier.urihttp://salesiana.dossiersoluciones.com/handle/123456789/87568
dc.subjectChemical Physics
dc.titleAb initio thermochemistry beyond chemical accuracy for first-and second-row compounds
dc.typetext

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