Henderson Thomas M, Izmaylov Artur F, Scalmani Giovanni, Scuseria Gustavo E
Department of Chemistry, Rice University, 6100 Main Street, Houston, Texas 77005-1892, USA.
J Chem Phys. 2009 Jul 28;131(4):044108. doi: 10.1063/1.3185673.
Long-range-corrected hybrids, which incorporate all of the long-range exact exchange interaction, improve performance for a host of molecular properties. The long-range portion of exact exchange is both computationally and formally problematic in solids, and screened hybrids therefore eliminate it. While screened hybrids give similar results to their parent global hybrids for many molecular properties, one may worry that they perform poorly for those properties that are improved by the long-range-correction procedure. In this paper, we show that at least for the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid, this is not the case; for many properties improved by long-range-correction, screened hybrids and global hybrids deliver essentially the same results. We suggest that this is because screened hybrids and global hybrids have fundamentally the same many-electron self-interaction error. We also introduce some small revisions to our computational implementation of the HSE screened hybrid, and we recommend these revisions for future applications of HSE.
包含所有长程精确交换相互作用的长程校正杂化泛函,能改善许多分子性质的计算性能。精确交换的长程部分在固体计算中存在计算和形式上的问题,因此筛选杂化泛函将其消除。虽然筛选杂化泛函在许多分子性质上给出的结果与其母体全局杂化泛函相似,但人们可能担心它们在那些通过长程校正程序得到改善的性质上表现不佳。在本文中,我们表明至少对于Heyd-Scuseria-Ernzerhof(HSE)筛选杂化泛函而言,情况并非如此;对于许多通过长程校正得到改善的性质,筛选杂化泛函和全局杂化泛函给出的结果基本相同。我们认为这是因为筛选杂化泛函和全局杂化泛函在本质上具有相同的多电子自相互作用误差。我们还对HSE筛选杂化泛函的计算实现进行了一些小的修正,并建议在HSE的未来应用中采用这些修正。