Self-interaction corrected SCAN functional for molecules and solids in the numeric atom-center orbital framework.
Self-interaction corrected SCAN functional for molecules and solids in the numeric atom-center orbital framework.
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DOI：
10.1063/5.0178075
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发表时间：
2024-01
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影响因子：
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通讯作者：
Sheng Bi;Christian Carbogno;Igor Ying Zhang;Matthias Scheffler
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作者：
Sheng Bi;Christian Carbogno;Igor Ying Zhang;Matthias Scheffler
半局域密度泛函近似 (DFA)，包括最先进的 SCAN 泛函，都受到自相互作用误差 (SIE) 的困扰。虽然这个错误仅针对单电子系统明确定义，但它启发了 Perdew 和 Zunger 提出的自相互作用校正方法（PZ-SIC），该方法在减轻多电子 SIE 方面显示出了希望。然而，PZ-SIC 方法以其显着的数值不稳定性而闻名。在这项研究中，我们引入了一种新颖的约束，该约束有助于本着 Edmiston-Ruedenberg 轨道的精神对 SIC 轨道进行自洽定域化 [Rev.1]。模组。物理。 35, 457 (1963)]。我们在全电子数字原子中心轨道代码 FHI-aims 中的实际实现保证了分子和固体的自洽 PZ-SIC 方程的高效和稳定收敛。我们进一步证明，我们的 PZ-SIC 方法有效地减轻了元广义梯度近似 SCAN 函数中的 SIE，显着提高了各种分子和固体选择的电离势、电荷转移能和带隙的准确性。然而，我们的 PZ-SIC 方法确实有其局限性。它无法改善我们测试集中已经准确的内聚能、晶格常数和体积模量等属性的扫描结果。这凸显了对具有更全面适用性的新一代DFA的需求。
Semilocal density-functional approximations (DFAs), including the state-of-the-art SCAN functional, are plagued by the self-interaction error (SIE). While this error is explicitly defined only for one-electron systems, it has inspired the self-interaction correction method proposed by Perdew and Zunger (PZ-SIC), which has shown promise in mitigating the many-electron SIE. However, the PZ-SIC method is known for its significant numerical instability. In this study, we introduce a novel constraint that facilitates self-consistent localization of the SIC orbitals in the spirit of Edmiston-Ruedenberg orbitals [Rev. Mod. Phys. 35, 457 (1963)]. Our practical implementation within the all-electron numeric atom-centered orbitals code FHI-aims guarantees efficient and stable convergence of the self-consistent PZ-SIC equations for both molecules and solids. We further demonstrate that our PZ-SIC approach effectively mitigates the SIE in the meta-generalized gradient approximation SCAN functional, significantly improving the accuracy for ionization potentials, charge-transfer energies, and bandgaps for a diverse selection of molecules and solids. However, our PZ-SIC method does have its limitations. It cannot improve the already accurate SCAN results for properties such as cohesive energies, lattice constants, and bulk modulus in our test sets. This highlights the need for new-generation DFAs with more comprehensive applicability.