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

被引:59
作者
Csonka, GI [1 ]
Johnson, BG
机构
[1] Tech Univ Budapest, Dept Inorgan Chem, H-1521 Budapest, Hungary
[2] Q Chem Inc, Pittsburgh, PA 15218 USA
关键词
hydrogen abstraction reaction barrier; self-interaction components; B3LYP and B3PW functionals; self-interaction corrected molecular geometries; self-interaction corrected total energies;
D O I
10.1007/s002140050318
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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 functionals with errors of 1.5, 2.9 and 3.0 kcal/mol, respectively.
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页码:158 / 165
页数:8
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