Theoretical Chemistry Accounts

, Volume 99, Issue 3, pp 158–165

Inclusion of exact exchange for self-interaction corrected H3 density functional potential energy surface

  • Gabor I. Csonka
  • Benny G. Johnson
Regular article

DOI: 10.1007/s002140050318

Cite this article as:
Csonka, G. & Johnson, B. Theor Chem Acc (1998) 99: 158. doi:10.1007/s002140050318

Abstract.

The effect of the inclusion of the exact exchange into self-interaction corrected generalized gradient approximation density functional theory (GGA-DFT) for the simplest hydrogen abstraction reaction, H + H2 → H3 → H2 + H, is presented using a triple-zeta augmented 6-311++G(d,3pd) basis set. The introduction of the self-interaction correction has a considerably larger effect on molecular geometry and vibrational frequencies than the inclusion of the exact exchange. We investigate the influence of the self-interaction error on the shape of the potential energy surface around the transition state of the hydrogen abstraction reaction. The decomposition of the self-interaction error into correlation and exchange parts shows that the exchange self-interaction error is the main component of the energy barrier error. The best agreements with the experimental barrier height were achieved by self-interaction corrected B3LYP, B-LYP and B3PW functionals with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.

Key words: Hydrogen abstraction reaction barrier Self-interaction components B3LYP and B3PW functionals Self-interaction corrected molecular geometries Self-interaction corrected total energies 

Copyright information

© Springer-Verlag Berlin Heidelberg 1998

Authors and Affiliations

  • Gabor I. Csonka
    • 1
  • Benny G. Johnson
    • 2
  1. 1.Department of Inorganic Chemistry, Technical University of Budapest, H-1521 Budapest, HungaryHU
  2. 2.Q-Chem Inc., 317 Whipple Street, Pittsburgh, PA 15218, USAUS

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