Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials.
Increasing the applicability of density functional theory. IV. Consequences of ionization-potential improved exchange-correlation potentials.
复制标题
增加密度泛函理论的适用性。
DOI：
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发表时间：
2014
影响因子：
4.4
通讯作者：
R. Bartlett
中科院分区：
文献类型：
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作者：
P. Verma;R. Bartlett
本文的目标是创建一个“一致的”平均场的Kohn-Sham（KS）密度泛函理论（DFT），这意味着泛函不仅应该提供良好的总能量特性，而且相应的KS本征值应该是分子垂直电离势（VIP）的精确近似，因为后一个条件证明了交换相关势（VXC）的可行性。没有突出使用的DFT方法显示这些属性：优化的有效电位VXC的从头算DFT。一个本地的，距离分离的混合势cam-QTP-00的基础上介绍了一个“一致的”KS DFT方法。计算出的VIP作为KS本征值的负值，对于一组广泛的分子的电子电离，包括核心，平均绝对误差为0.8 eV。势垒高度，平衡几何形状，并从潜在的磁性得到与实验符合得很好。通过使用QTP-00方法的非变分全局混合变体，可以实现类似的精度和更少的计算工作。
This paper's objective is to create a "consistent" mean-field based Kohn-Sham (KS) density functional theory (DFT) meaning the functional should not only provide good total energy properties, but also the corresponding KS eigenvalues should be accurate approximations to the vertical ionization potentials (VIPs) of the molecule, as the latter condition attests to the viability of the exchange-correlation potential (VXC). None of the prominently used DFT approaches show these properties: the optimized effective potential VXC based ab initio dft does. A local, range-separated hybrid potential cam-QTP-00 is introduced as the basis for a "consistent" KS DFT approach. The computed VIPs as the negative of KS eigenvalue have a mean absolute error of 0.8 eV for an extensive set of molecule's electron ionizations, including the core. Barrier heights, equilibrium geometries, and magnetic properties obtained from the potential are in good agreement with experiment. A similar accuracy with less computational efforts can be achieved by using a non-variational global hybrid variant of the QTP-00 approach.