Department of Chemistry, University of Illinois at Urbana-Champaign , 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
J Phys Chem A. 2014 Jan 30;118(4):655-72. doi: 10.1021/jp410587b. Epub 2013 Dec 26.
Second-order many-body perturbation theory [MBPT(2)] is the lowest-ranked member of a systematic series of approximations convergent at the exact solutions of the Schrödinger equations. It has served and continues to serve as the testing ground for new approximations, algorithms, and even theories. This article introduces this basic theory from a variety of viewpoints including the Rayleigh-Schrödinger perturbation theory, the many-body Green's function theory based on the Dyson equation, and the related Feynman-Goldstone diagrams. It also explains the important properties of MBPT(2) such as size consistency, its ability to describe dispersion interactions, and divergence in metals. On this basis, this article surveys three major advances made recently by the authors to this theory. They are a finite-temperature extension of MBPT(2) and the resolution of the Kohn-Luttinger conundrum, a stochastic evaluation of the correlation and self-energies of MBPT(2) using the Monte Carlo integration of their Laplace-transformed expressions, and an extension to anharmonic vibrational zero-point energies and transition frequencies based on the Dyson equation.
二阶多体微扰理论(MBPT(2))是薛定谔方程精确解的一系列系统逼近中排名最低的成员。它曾是、现在也是新近似、算法,甚至理论的测试平台。本文从瑞利-薛定谔微扰理论、基于狄拉克方程的多体格林函数理论以及相关的费曼-戈德斯通图等多个角度介绍了这一基本理论。它还解释了 MBPT(2)的重要性质,如大小一致性、描述色散相互作用的能力以及金属中的发散性。在此基础上,本文综述了作者最近对该理论的三项重大进展。它们是 MBPT(2)的有限温度扩展以及解决科恩-卢廷格难题,使用它们的拉普拉斯变换表达式的蒙特卡罗积分对 MBPT(2)的相关和自能进行随机评估,以及基于狄拉克方程扩展到非谐振动零点能和跃迁频率。