论文标题
通过约束提高密度函数近似值的交换和相关潜力
Improving the exchange and correlation potential in density functional approximations through constraints
论文作者
论文摘要
我们审查并扩展了我们的工作,以对局部和半局部密度函数近似的有效Kohn Sham(KS)构成限制。在这项工作中,我们放宽了先前强加的阳性限制,这增加了计算成本,我们发现这样做是安全的,除了很少的电子系统。受约束的最小化总是导致解决优化有效电位(OEP)方程的解决方案,以确定KS电位。我们简要审查了我们先前在此问题上的工作,并以许多示例演示了,尽管OEP的数学问题有有限的基础,但我们的OEP方程仍然表现得很好。我们证明,限制Hartree的筛选电荷,交换和相关潜力不仅纠正其渐近行为,而且还允许交换和相关潜力表现出非零导数不连续性,这是确切的KS潜力的特征,这对于在固体中准确预测的固体中的精确预测很难捕获半元素近似值的精确预测。
We review and expand on our work to impose constraints on the effective Kohn Sham (KS) potential of local and semi-local density functional approximations. In this work, we relax a previously imposed positivity constraint, which increased the computational cost and we find that it is safe to do so, except in systems with very few electrons. The constrained minimisation leads invariably to the solution of an optimised effective potential (OEP) equation in order to determine the KS potential. We review briefly our previous work on this problem and demonstrate with numerous examples that despite well-known mathematical issues of the OEP with finite basis sets, our OEP equations are well behaved. We demonstrate that constraining the screening charge of the Hartree, exchange and correlation potential not only corrects its asymptotic behaviour but also allows the exchange and correlation potential to exhibit nonzero derivative discontinuity, a feature of the exact KS potential that is necessary for the accurate prediction of band-gaps in solids but very hard to capture with semi-local approximations.