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Gaussian-3 (G3) theory for molecules containing first and second-row atoms

J. Chem. Phys. 109, 7764 (1998); doi:10.1063/1.477422

Issue Date: 8 November 1998

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Larry A. Curtiss
Chemistry and Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois 60439

Krishnan Raghavachari
Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974

Paul C. Redfern
Chemistry and Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois 60439

Vitaly Rassolov and John A. Pople
Department of Chemistry, Northwestern University, Evanston, Illinois 60208
Gaussian-3 theory (G3 theory) for the calculation of molecular energies of compounds containing first (Li–F) and second row (Na–Cl) atoms is presented. This new theoretical procedure, which is based on ab initio molecular-orbital theory, modifies G2 theory [J. Chem. Phys. 94, 7221 (1991)] in several ways including a new sequence of single point energy calculations using different basis sets, a new formulation of the higher level correction, a spin–orbit correction for atoms, and a correction for core correlation. G3 theory is assessed using 299 energies from the G2/97 test set including enthalpies of formation, ionization potentials, electron affinities, and proton affinities. This new procedure corrects many of the deficiencies of G2 theory. There is a large improvement for nonhydrogen systems such as SiF4 and CF4, substituted hydrocarbons, and unsaturated cyclic species. Core-related correlation is found to be a significant factor, especially for species with unsaturated rings. The average absolute deviation from experiment for the 148 calculated enthalpies of formation is reduced to under one kcal/mol, from 1.56 kcal/mol for G2 theory to 0.94 kcal/mol for G3 theory. Significant improvement is also found for ionization potentials and electron affinities. The overall average absolute deviation of G3 theory from experiment for the 299 energies is 1.02 kcal/mol compared to 1.48 kcal/mol for G2 theory. ©1998 American Institute of Physics.
History: Received 9 June 1998; accepted 22 July 1998
Permalink: http://link.aip.org/link/?JCPSA6/109/7764/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ar
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Ab initio calculations
  • YEAR: 1998

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (38)
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