Negative Electron Affinities and Derivative Discontinuity Contribution from a Generalized Gradient Approximation Exchange Functional
Negative Electron Affinities and Derivative Discontinuity Contribution from a Generalized Gradient Approximation Exchange Functional
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DOI：
10.1021/acs.jpca.9b10956
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发表时间：
2020-02-20
影响因子：
2.9
通讯作者：
Trickey, S. B.
中科院分区：
文献类型：
--
作者：
Carmona-Espindola, Javier;Gazquez, Jose L.;Trickey, S. B.
提出了两种从基态密度泛函方法系统地计算负电子亲合能的方法。一个是利用最低未占分子轨道的能量位移提供的近似包含导数不连续的近正确渐近势（NCAP）的非经验，约束为基础的广义梯度近似交换功能。另一种是基于NCAP交换关联势的导数间断的二阶微扰计算。对一组38个分子，NCAP导致一个相当准确的描述，进一步提高通过微扰校正。结果表明，在计算负电子亲和势的交换相关势的渐近行为的重要性，以及展示的通用性的NCAP功能。
Two methods to calculate negative electron affinities systematically from ground-state density functional methods are presented. One makes use of the lowest unoccupied molecular orbital energy shift provided by approximate inclusion of derivative discontinuity in the nearly correct asymptotic potential (NCAP) nonempirical, constraint-based generalized gradient approximation exchange functional. The other uses a second-order perturbation calculation of the derivative discontinuity based on the NCAP exchange-correlation potential. On a set of thirty-eight molecules, NCAP leads to a rather accurate description that is improved further through the perturbation correction. The results presented show the importance of the asymptotic behavior of the exchange-correlation potential in the calculation of negative electron affinities as well as demonstrating the versatility of the NCAP functional.