Li Chen, Zheng Xiao, Cohen Aron J, Mori-Sánchez Paula, Yang Weitao
Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, China.
Phys Rev Lett. 2015 Feb 6;114(5):053001. doi: 10.1103/PhysRevLett.114.053001. Epub 2015 Feb 4.
Delocalization error is one of the most fundamental and dominant errors that plagues presently used density functional approximations. It is responsible for a large class of problems in the density functional theory calculations. For an effective and universal alleviation of the delocalization error, we develop a local scaling correction scheme by imposing the Perdew-Parr-Levy- Balduz linearity condition to local regions of a system. Our novel scheme is applicable to various mainstream density functional approximations. It substantially reduces the delocalization error, as exemplified by the significantly improved description of dissociating molecules, transition-state species, and charge-transfer systems. The usefulness of our novel scheme affirms that the explicit treatment of fractional electron distributions is essentially important for reducing the intrinsic delocalization error associated with approximate density functionals.
离域误差是困扰当前使用的密度泛函近似方法的最基本且最主要的误差之一。它在密度泛函理论计算中导致了一大类问题。为了有效且普遍地减轻离域误差，我们通过将佩德韦 - 帕尔 - 利维 - 巴尔杜兹线性条件应用于系统的局部区域，开发了一种局部缩放校正方案。我们的新方案适用于各种主流的密度泛函近似方法。它显著降低了离域误差，以对解离分子、过渡态物种和电荷转移系统的显著改进描述为例。我们新方案的有效性证实了对分数电子分布的显式处理对于减少与近似密度泛函相关的固有离域误差至关重要。
