### 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 + H_{2} → H_{3} → H_{2} + 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 functional with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.

Original language | English |
---|---|

Pages (from-to) | 158-165 |

Number of pages | 8 |

Journal | Theoretical Chemistry Accounts |

Volume | 99 |

Issue number | 3 |

Publication status | Published - May 1998 |

### Fingerprint

### Keywords

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

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

_{3}density functional potential energy surface.

*Theoretical Chemistry Accounts*,

*99*(3), 158-165.

**Inclusion of exact exchange for self-interaction corrected H _{3} density functional potential energy surface.** / Csonka, G.; Johnson, Benny G.

Research output: Contribution to journal › Article

_{3}density functional potential energy surface',

*Theoretical Chemistry Accounts*, vol. 99, no. 3, pp. 158-165.

_{3}density functional potential energy surface. Theoretical Chemistry Accounts. 1998 May;99(3):158-165.

}

TY - JOUR

T1 - Inclusion of exact exchange for self-interaction corrected H3 density functional potential energy surface

AU - Csonka, G.

AU - Johnson, Benny G.

PY - 1998/5

Y1 - 1998/5

N2 - 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 functional with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.

AB - 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 functional with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.

KW - B3LYP and B3PW functionals

KW - Hydrogen abstraction reaction barrier

KW - Self-interaction components

KW - Self-interaction corrected molecular geometries

KW - Self-interaction corrected total energies

UR - http://www.scopus.com/inward/record.url?scp=0032383471&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0032383471&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0032383471

VL - 99

SP - 158

EP - 165

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

SN - 1432-881X

IS - 3

ER -