论文标题
朝着解决Perdew-Zunger自我交往校正的悖论方向的方向。 ii。能量密度的仪表一致性在三个近似级别
A Step in the Direction of Resolving the Paradox of Perdew-Zunger Self-interaction Correction. II. Gauge Consistency of the Energy Density at Three Levels of Approximation
论文作者
论文摘要
perdew-zunger(PZ)自我交流校正(SIC)旨在校正交换 - 相关(XC)能量的任何近似密度功能的单电子极限(XC)能量,同时对确切功能均未校正。不幸的是,它破坏了未校正的近似功能的缓慢变化的空间限制,其中这些功能是正确的。可以通过在许多电子区域中局部缩减PZ SIC的能量密度来恢复正确的限制,但是除非在同一指数中表达PZ SIC SIC能量密度的自我锻炼和精确的自XC项,否则将发现对确切功能的虚假校正。 Only the local density approximation satisfies the same-gauge condition for the energy density, which explains why the recent local-scaling SIC (LSIC) is found here to work excellently for atoms and molecules only with this basic approximation, and not with the more advanced generalized gradient approximations (GGAs) and meta-GGAs, which lose the Hartree gauge via simplifying integrations by parts.达到精确XC功能的Hartree量规的能量密度的转换也可以应用于近似功能。这样做会导致简单的缩小自身相互作用(SDSIC)校正,通常在许多分子特性(包括平衡键长)的测试中比PZ SIC准确得多。目前的工作明确表明,可以通过恢复其正确的缓慢变化密度限制来消除在三个级别上应用于标准功能的PZ SIC的最大误差。它还证实了这些限制与原子和分子的相关性。
The Perdew-Zunger(PZ) self-interaction correction (SIC) was designed to correct the one-electron limit of any approximate density functional for the exchange-correlation (xc) energy, while yielding no correction to the exact functional. Unfortunately, it spoils the slowly-varying-in-space limits of the uncorrected approximate functionals, where those functionals are right by construction. The right limits can be restored by locally scaling down the energy density of the PZ SIC in many-electron regions, but then a spurious correction to the exact functional would be found unless the self-Hartree and exact self-xc terms of the PZ SIC energy density were expressed in the same gauge. Only the local density approximation satisfies the same-gauge condition for the energy density, which explains why the recent local-scaling SIC (LSIC) is found here to work excellently for atoms and molecules only with this basic approximation, and not with the more advanced generalized gradient approximations (GGAs) and meta-GGAs, which lose the Hartree gauge via simplifying integrations by parts. The transformation of energy density that achieves the Hartree gauge for the exact xc functional can also be applied to approximate functionals. Doing so leads to a simple scaled-down self-interaction (sdSIC) correction that is typically much more accurate than PZ SIC in tests for many molecular properties (including equilibrium bond lengths). The present work shows unambiguously that the largest errors of PZ SIC applied to standard functionals at three levels of approximation can be removed by restoring their correct slowly-varying-density limits. It also confirms the relevance of these limits to atoms and molecules.