Jin Ye, Zhang Du, Chen Zehua, Su Neil Qiang, Yang Weitao
Department of Chemistry, Duke University , Durham, North Carolina 27708, United States.
J Phys Chem Lett. 2017 Oct 5;8(19):4746-4751. doi: 10.1021/acs.jpclett.7b02165. Epub 2017 Sep 18.
A new self-consistent procedure for calculating the total energy with an orbital-dependent density functional approximation (DFA), the generalized optimized effective potential (GOEP), is developed in the present work. The GOEP is a nonlocal Hermitian potential that delivers the sets of occupied and virtual orbitals and minimizes the total energy. The GOEP optimization leads to the same minimum as does the orbital optimization. The GOEP method is promising as an effective optimization approach for orbital-dependent functionals, as demonstrated for the self-consistent calculations of the random phase approximation (RPA) to the correlation functionals in the particle-hole (ph) and particle-particle (pp) channels. The results show that the accuracy in describing the weakly interacting van der Waals systems is significantly improved in the self-consistent calculations. In particular, the important single excitations contribution in non-self-consistent RPA calculations can be captured self-consistently through the GOEP optimization, leading to orbital renormalization, without using the single excitations in the energy functional.
在本工作中，开发了一种新的自洽程序，用于使用轨道依赖密度泛函近似（DFA）计算总能量，即广义优化有效势（GOEP）。GOEP是一种非局部厄米势，它给出占据轨道和虚轨道集，并使总能量最小化。GOEP优化导致与轨道优化相同的最小值。GOEP方法有望成为一种用于轨道依赖泛函的有效优化方法，如在粒子 - 空穴（ph）和粒子 - 粒子（pp）通道中对相关泛函的随机相位近似（RPA）的自洽计算所示。结果表明，在自洽计算中，描述弱相互作用范德华系统的精度有显著提高。特别是，通过GOEP优化可以自洽地捕获非自洽RPA计算中重要的单激发贡献，从而导致轨道重整化，而无需在能量泛函中使用单激发。
