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Keld L. Bak

Chemical accuracy from 'Coulomb hole' extrapolated molecular quantum-mechanical calculations

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In standard ab initio molecular quantum-mechanical calculations it is difficult, if at all possible, to calculate fundamental chemical properties like atomisation energies and reaction enthalpies to the chemical accuracy of 1 kcal/mol approximate to 4 M/mol. The principal obstacle is the presence of the Coulomb hole in the electronic wave function, whose description converges slowly with the size of the basis set. From a systematic sequence of basis-set calculations, we demonstrate that physically motivated extrapolations can be used to accelerate the basis-set convergence significantly and that, for highly correlated wave functions, chemical accuracy is obtained even with medium-sized basis sets when the extrapolation is used. (C) 2001 Elsevier Science B.V. All rights reserved.

Original languageEnglish
JournalJournal of Molecular Structure: THEOCHEM
Volume567
Pages (from-to)375-384
Number of pages10
ISSN0166-1280
Publication statusPublished - 13 Jun 2001

    Research areas

  • molecular electronic structure, basis-set extrapolation, chemical accuracy, atomisation energies, reaction enthalpies, BASIS-SET CONVERGENCE, GAUSSIAN-BASIS SETS, PLESSET PERTURBATION-THEORY, TOTAL ATOMIZATION ENERGIES, ELECTRONIC-STRUCTURE, CONFIGURATION-INTERACTION, CORRELATED CALCULATIONS, WAVE-FUNCTIONS, STANDARD, HYDROGEN

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