Department of Chemistry and Biochemistry , University of California, Santa Barbara , Santa Barbara , California 93106 , United States.
J Chem Theory Comput. 2019 Nov 12;15(11):6254-6266. doi: 10.1021/acs.jctc.9b00317. Epub 2019 Oct 8.
New stochastic approaches for the computation of electronic excitations are developed within the many-body perturbation theory. Three approximations to the electronic self-energy are considered: , , and Γ. All three methods are formulated in the time domain, and the latter two incorporate nonlocal vertex corrections. In the case of Γ, the vertex corrections are included both in the screened Coulomb interaction and in the expression for the self-energy. The implementation of the three approximations is verified by comparison to deterministic results for a set of small molecules. The performance of the fully stochastic implementation is tested on acene molecules, C and PCBM. The vertex correction appears crucial for the description of unoccupied states. Unlike conventional (deterministic) approaches, all three stochastic methods scale linearly with the number of electrons.
新的随机方法被开发出来用于多体微扰理论中的电子激发计算。考虑了电子自能的三种近似方法: , 和 Γ 。所有三种方法都是在时域中进行公式化的,后两种方法包含了非局域顶点修正。对于 Γ ,顶点修正既包含在屏蔽库仑相互作用中,也包含在自能的表达式中。三种近似方法的实现通过与一组小分子的确定性结果进行比较得到验证。完全随机实现的性能在并五苯分子 C 和 PCBM 上进行了测试。顶点修正对于未占据态的描述至关重要。与传统的(确定性)方法不同,所有三种随机方法都与电子数呈线性关系。