DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE
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DOI：
10.1063/1.464913
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发表时间：
1993-04-01
影响因子：
4.4
通讯作者：
BECKE, AD
中科院分区：
文献类型：
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作者：
BECKE, AD
尽管具有交换相关性梯度修正的Kohn-Sham密度泛函理论具有显著的热化学准确性[例如，参见A. D. Becke， J. Chem]。我们认为，除非考虑到精确交换信息，否则进一步的改进是不可能的。提出了支持这一观点的论据，并在第一和第二行体系的56个原子化能、42个电离势、8个质子亲和和10个总原子能上测试了包含局域自旋密度、梯度和精确交换项的半经验交换相关泛函。该泛函的性能明显优于先前仅具有梯度校正的泛函，并且与实验雾化能的平均绝对偏差非常小，仅为2.4 kcal/mol。
Despite the remarkable thermochemical accuracy of Kohn-Sham density-functional theories with gradient corrections for exchange-correlation [see, for example, A. D. Becke, J. Chem. Phys. 96, 2155 (1992)], we believe that further improvements are unlikely unless exact-exchange information is considered. Arguments to support this view are presented, and a semiempirical exchange-correlation functional containing local-spin-density, gradient, and exact-exchange terms is tested on 56 atomization energies, 42 ionization potentials, 8 proton affinities, and 10 total atomic energies of first- and second-row systems. This functional performs significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.