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Gaussian-3 theory using density functional geometries and zero-point energies

J. Chem. Phys. 110, 7650 (1999); doi:10.1063/1.478676

Issue Date: 22 April 1999

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Anwar G. Baboul, Larry A. Curtiss, and Paul C. Redfern
Chemistry and Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois 60439

Krishnan Raghavachari
Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974
A variation of Gaussian-3 (G3) theory is presented in which the geometries and zero-point energies are obtained from B3LYP density functional theory [B3LYP/6-31G(d)] instead of geometries from second-order perturbation theory [MP2(FU)/6-31G(d)] and zero-point energies from Hartree–Fock theory [HF/6-31G(d)]. This variation, referred to as G3//B3LYP, is assessed on 299 energies (enthalpies of formation, ionization potentials, electron affinities, proton affinities) from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The G3//B3LYP average absolute deviation from experiment for the 299 energies is 0.99 kcal/mol compared to 1.01 kcal/mol for G3 theory. Generally, the results from the two methods are similar, with some exceptions. G3//B3LYP theory gives significantly improved results for several cases for which MP2 theory is deficient for optimized geometries, such as CN and O<sub>2</sub><sup> + </sup>. However, G3//B3LYP does poorly for ionization potentials that involve a Jahn–Teller distortion in the cation (CH<sub>4</sub><sup> + </sup>, BF<sub>3</sub><sup> + </sup>, BCl<sub>3</sub><sup> + </sup>) because of the B3LYP/6-31G(d) geometries. The G3(MP2) method is also modified to use B3LYP/6-31G(d) geometries and zero-point energies. This variation, referred to as G3(MP2)//B3LYP, has an average absolute deviation of 1.25 kcal/mol compared to 1.30 kcal/mol for G3(MP2) theory. Thus, use of density functional geometries and zero-point energies in G3 and G3(MP2) theories is a useful alternative to MP2 geometries and HF zero-point energies. ©1999 American Institute of Physics.
History: Received 9 December 1998; accepted 23 December 1998
Permalink: http://link.aip.org/link/?JCPSA6/110/7650/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ew
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Density-functional theory
  • 31.15.Md
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Perturbation theory
  • 31.15.Ne
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Self-consistent-field methods
  • 82.60.Cx
    Physical chemistry Chemical thermodynamics Enthalpies of combustion, reaction, and formation
  • 32.10.Hq
    Atomic properties and interactions with photons Properties of atoms and atomic ions Ionization potentials, electron affinities
  • 33.15.Ry
    Molecular properties and interactions with photons Properties of molecules and molecular ions Ionization potentials, electron affinities, molecular core binding energy
  • YEAR: 1999

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (28)
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