Janesko Benjamin G, Krukau Aliaksandr V, Scuseria Gustavo E
Department of Chemistry, Rice University, Houston, Texas 77005, USA.
J Chem Phys. 2008 Sep 28;129(12):124110. doi: 10.1063/1.2980056.
We present local hybrid functionals that incorporate a position-dependent admixture of short-range (screened) nonlocal exact [Hartree-Fock-type (HF)] exchange. We test two limiting cases: screened local hybrids with no long-range HF exchange and long-range-corrected local hybrids with 100% long-range HF exchange. Long-range-corrected local hybrids provide the exact asymptotic exchange-correlation potential in finite systems, while screened local hybrids avoid the problems inherent to long-range HF exchange in metals and small-bandgap systems. We treat these functionals self-consistently using the nonlocal exchange potential constructed from Kohn-Sham orbital derivatives. Generalized Kohn-Sham calculations with screened and long-range-corrected local hybrids can provide accurate molecular thermochemistry and kinetics, comparable to existing local hybrids of full-range exchange. Generalized Kohn-Sham calculations with existing full-range local hybrids provide results consistent with previous non-self-consistent and "localized local hybrid" calculations. These new functionals appear to provide a promising extension of existing local and range-separated hybrids.
我们提出了局部杂化泛函，其包含短程（屏蔽）非局部精确[哈特里 - 福克型（HF）]交换的位置相关混合。我们测试了两种极限情况：无长程HF交换的屏蔽局部杂化泛函和具有100%长程HF交换的长程校正局部杂化泛函。长程校正局部杂化泛函在有限体系中提供了精确的渐近交换相关势，而屏蔽局部杂化泛函避免了金属和小带隙体系中长程HF交换所固有的问题。我们使用由科恩 - Sham轨道导数构建的非局部交换势自洽地处理这些泛函。使用屏蔽和长程校正局部杂化泛函的广义科恩 - Sham计算可以提供准确的分子热化学和动力学，与现有的全范围交换局部杂化泛函相当。使用现有的全范围局部杂化泛函进行的广义科恩 - Sham计算提供的结果与先前的非自洽和“局域化局部杂化”计算一致。这些新的泛函似乎为现有的局部和范围分离杂化泛函提供了有前景的扩展。
