A DENSITY-FUNCTIONAL STUDY OF THE SIMPLEST HYDROGEN ABSTRACTION REACTION - EFFECT OF SELF-INTERACTION CORRECTION

Citation
Bg. Johnson et al., A DENSITY-FUNCTIONAL STUDY OF THE SIMPLEST HYDROGEN ABSTRACTION REACTION - EFFECT OF SELF-INTERACTION CORRECTION, Chemical physics letters, 221(1-2), 1994, pp. 100-108
Citations number
55
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
Journal title
ISSN journal
00092614
Volume
221
Issue
1-2
Year of publication
1994
Pages
100 - 108
Database
ISI
SICI code
0009-2614(1994)221:1-2<100:ADSOTS>2.0.ZU;2-6
Abstract
Twenty-four different local and gradient-corrected density functional methods were used in a study of the reaction H+H-2-->H-2+H. Barrier he ights were calculated with a large basis set. The results were compare d to those obtained by ab initio methods and experiment. It was found that conventional Kohn-Sham methods consistently and significantly und erestimate the reaction barrier. In particular, the local spin-density approximation (LSDA) in unmodified form completely fails, predicting H-3 to be a stable species. However, the inclusion of a self-interacti on correction restores the correct qualitative features of the potenti al surface, and generally leads to reasonable results when pairing a g radient-corrected exchange functional with a correlation functional.