Zhan Jiawei, Govoni Marco, Galli Giulia
Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States.
Materials Science Division and Center for Molecular Engineering, Argonne National Laboratory, Lemont, Illinois 60439, United States.
J Chem Theory Comput. 2023 Sep 12;19(17):5851-5862. doi: 10.1021/acs.jctc.3c00580. Epub 2023 Aug 17.
Electronic structure calculations based on density functional theory (DFT) have successfully predicted numerous ground-state properties of a variety of molecules and materials. However, exchange and correlation functionals currently used in the literature, including semilocal and hybrid functionals, are often inaccurate to describe the electronic properties of heterogeneous solids, especially systems composed of building blocks with large dielectric mismatch. Here, we present a dielectric-dependent range-separated hybrid functional, screened-exchange range-separated hybrid (SE-RSH), for the investigation of heterogeneous materials. We define a spatially dependent fraction of exact exchange inspired by the static Coulomb-hole and screened-exchange (COHSEX) approximation used in many-body perturbation theory, and we show that the proposed functional accurately predicts the electronic structure of several nonmetallic interfaces, three- and two-dimensional, pristine, and defective solids and nanoparticles.
基于密度泛函理论（DFT）的电子结构计算已成功预测了各种分子和材料的众多基态性质。然而，目前文献中使用的交换关联泛函，包括半局域泛函和杂化泛函，在描述非均匀固体的电子性质时往往不准确，尤其是由具有大介电失配的结构单元组成的体系。在此，我们提出一种依赖于介电常数的范围分离杂化泛函——屏蔽交换范围分离杂化（SE-RSH）泛函，用于研究非均匀材料。我们受多体微扰理论中使用的静态库仑空穴和屏蔽交换（COHSEX）近似启发，定义了一个空间相关的精确交换分数，并且我们表明所提出的泛函能够准确预测几种非金属界面、三维和二维的原始及缺陷固体以及纳米颗粒的电子结构。
