Importance of the correlation contribution for local hybrid functionals: Range separation and self-interaction corrections
Importance of the correlation contribution for local hybrid functionals: Range separation and self-interaction corrections
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DOI：
10.1063/1.3672080
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发表时间：
2012-01-07
影响因子：
4.4
通讯作者：
Kaupp, Martin
中科院分区：
文献类型：
--
作者：
Arbuznikov, Alexei V.;Kaupp, Martin
局部杂化泛函及其位置相关的精确交换混合是杂化泛函概念的一个简单而有希望的推广。基于局域自旋密度近似(LSDA)和精确交换的简单混合的局域杂化材料已经被证明在热化学、反应势垒和一系列其他性质方面是成功的。到目前为止，这一代局域杂化与LSDA关联泛函的组合被发现对原子化能量和支配精确交换混合物的一系列局域混合函数(LMF)给出了最有利的结果。在这里，我们表明，用于局部混合交换的相关泛函的选择对交换部分的参数化以及整体性能也有重要影响。基于(I)将LSDA关联分离为短程(SR)和长程(LR)部分，以及(Ii)部分或完全消除SR部分的单电子自相关，提出了一种新的局部杂交种相关部分的ANATZ。结果表明，这种修正的关联泛函允许在热化学竞争的局部杂化中比以前有更大的精确交换混合物。这导致了反应势垒和受自相互作用误差关键影响的其他性质的改善，如许多例子所证明的那样。基于射程分离方法，对关联能分解为动力学部分和非动力学部分提出了新的看法。(C)2012年美国物理研究所。[DOI：10.1063/1.3672080]
Local hybrid functionals with their position-dependent exact-exchange admixture are a conceptually simple and promising extension of the concept of a hybrid functional. Local hybrids based on a simple mixing of the local spin density approximation (LSDA) with exact exchange have been shown to be successful for thermochemistry, reaction barriers, and a range of other properties. So far, the combination of this generation of local hybrids with an LSDA correlation functional has been found to give the most favorable results for atomization energies, for a range of local mixing functions (LMFs) governing the exact-exchange admixture. Here, we show that the choice of correlation functional to be used with local hybrid exchange crucially influences the parameterization also of the exchange part as well as the overall performance. A novel ansatz for the correlation part of local hybrids is suggested based on (i) range-separation of LSDA correlation into short-range (SR) and long-range (LR) parts, and (ii) partial or full elimination of the one-electron self-correlation from the SR part. It is shown that such modified correlation functionals allow overall larger exact exchange admixture in thermochemically competitive local hybrids than before. This results in improvements for reaction barriers and for other properties crucially influenced by self-interaction errors, as demonstrated by a number of examples. Based on the range-separation approach, a fresh view on the breakdown of the correlation energy into dynamical and non-dynamical parts is suggested. (C) 2012 American Institute of Physics. [doi: 10.1063/1.3672080]