Density-functional thermochemistry. II. The effect of the Perdew–Wang generalized-gradient correlation correction.

In an earlier paper [A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], Kohn–Sham density-functional calculations of the total atomization energies of the 55 molecules of the Gaussian-1 database of Pople and co-workers [J. Chem. Phys. 90, 5622 (1989); 93, 2537 (1990)] were reported. We found that the local-spin-density exchange-correlation approximation with a ‘‘gradient correction’’ for exchange gave an average deviation from experiment of only 3.7 kcal/mol. In the present work we assess the role of gradient corrections for dynamical correlation, and we enlarge our earlier survey to include 42 atomic and molecular ionization potentials and 8 proton affinities as well. We conclude that gradient corrections for correlation do not improve atomization energies, but are vitally important in electron nonconserving processes such as ionization. [ABSTRACT FROM AUTHOR]