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

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.