DENSITY-FUNCTIONAL THERMOCHEMISTRY .2. THE EFFECT OF THE PERDEW-WANG GENERALIZED-GRADIENT CORRELATION CORRECTION
DENSITY-FUNCTIONAL THERMOCHEMISTRY .2. THE EFFECT OF THE PERDEW-WANG GENERALIZED-GRADIENT CORRELATION CORRECTION
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DOI：
10.1063/1.463343
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发表时间：
1992-12-15
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
在较早的一篇论文中[A. D.贝克，J.化学。物理。 96, 2155 (1992)]，Pople 及其同事的 Gaussian-1 数据库中 55 个分子的总原子化能的 Kohn-Sham 密度泛函计算 [J Chem. 96, 2155 (1992)]物理。 90, 5622 (1989); 93, 2537 (1990)] 进行了报道。我们发现，具有交换“梯度校正”的局域自旋密度交换相关近似与实验的平均偏差仅为 3.7 kcal/mol。在目前的工作中，我们评估了梯度校正对动态相关性的作用，并扩大了之前的调查范围，包括 42 个原子和分子电离势以及 8 个质子亲和势。我们得出的结论是，相关性的梯度校正不会提高原子化能量，但在电离等电子非守恒过程中至关重要。
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.