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

Abstract

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. {bold 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. {bold 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{endash}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 ({gt}1thinspeV). The BLYP density functionalmore » 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. {copyright} {ital 1998 American Institute of Physics.}« less

Authors:
;  [1];  [2];  [3]
  1. Chemistry Division/Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439-4828 (United States)
  2. Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974 (United States)
  3. Chemistry Department, Northwestern University, Evanston, Illinois 60208 (United States)
Publication Date:
OSTI Identifier:
636137
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 109; Journal Issue: 1; Other Information: PBD: Jul 1998
Country of Publication:
United States
Language:
English
Subject:
66 PHYSICS; IONIZATION POTENTIAL; AFFINITY; ELECTRONEGATIVITY; ATOMS; MOLECULES

Citation Formats

Curtiss, L A, Redfern, P C, Raghavachari, K, and Pople, J A. Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities. United States: N. p., 1998. Web. doi:10.1063/1.476538.
Curtiss, L A, Redfern, P C, Raghavachari, K, & Pople, J A. Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities. United States. doi:10.1063/1.476538.
Curtiss, L A, Redfern, P C, Raghavachari, K, and Pople, J A. Wed . "Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities". United States. doi:10.1063/1.476538.
@article{osti_636137,
title = {Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities},
author = {Curtiss, L A and Redfern, P C and Raghavachari, K and Pople, J A},
abstractNote = {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. {bold 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. {bold 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{endash}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 ({gt}1thinspeV). 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. {copyright} {ital 1998 American Institute of Physics.}},
doi = {10.1063/1.476538},
journal = {Journal of Chemical Physics},
number = 1,
volume = 109,
place = {United States},
year = {1998},
month = {7}
}