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Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities

J. Chem. Phys. 109, 42 (1998); doi:10.1063/1.476538

Issue Date: 1 July 1998

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Larry A. Curtiss and Paul C. Redfern
Chemistry Division/Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439-4828

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

John A. Pople
Chemistry Department, Northwestern University, Evanston, Illinois 60208
A set of 146 well-established ionization potentials and electron affinities is presented. This set, referred to as the G2 ion test set, includes the 63 atoms and molecules whose ionization potentials and electron affinities were used to test Gaussian-2 (G2) theory [J. Chem. Phys. 94, 7221 (1991)] and 83 new atoms and molecules. It is hoped that this new test set combined with the recently published test set of enthalpies of neutral molecules [J. Chem. Phys. 106, 1063 (1997)] will provide a means for assessing and improving theoretical models. From an assessment of G2 and density functional theories on this test set, it is found that G2 theory is the most reliable method. It has an average absolute deviation of 0.06 eV for both ionization potentials and electron affinities. The two modified versions of G2 theory, G2(MP2,SVP) and G2(MP2) theory, have average absolute deviations of 0.08–0.09 eV for both ionization potentials and electron affinities. The hybrid B3LYP density functional method has the smallest average absolute deviation (0.18 eV) of the seven density functional methods tested for ionization potentials. The largest deviation for the density functional methods is for the ionization potential of CN (> 1 eV). The BLYP density functional method has the smallest average absolute deviation (0.11 eV) of the seven density functional methods tested for electron affinities, while the BPW91, B3LYP, and B3PW91 methods also do quite well. ©1998 American Institute of Physics.
History: Received 29 December 1997; accepted 13 February 1998
Permalink: http://link.aip.org/link/?JCPSA6/109/42/1
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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
  • 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: 1998

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (33)
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