How Many-Body Perturbation Theory (MBPT) Has changed Quantum Chemistry

摘要

The history of many-body perturbation theory (MBPT) and its impact on Quantum Chemistry is reviewed, starting with Brueckner's conjecture of a linked-cluster expansion and the time-dependent derivation by Goldstone of such an expansion. A central part of this article is the time-independent formulation of quantum chemistry in Fock space and its diagrammatic representation including the particle-hole picture and the inversion of a commutator. The results of the time-independent derivation of MBPT are compared with those of Goldstone. It is analyzed which ingredients of Goldstone's approach are decisive. The connected diagram theorem is derived both in a constructive way based on a Lie-algebraic formulation and a nonconstructive way making use of the separation theorem. It is discussed why the Goldstone derivation starting from a unitary time-evolution operator, ends up with a wave operator in intermediate normalization. The Moller-Plesset perturbation expansions of Bartlett and Pople are compared. Examples of complete summations of certain classes of diagrams are discussed, for example, that which leads to the Bethe-Goldstone expansion. MBPT for energy differences is analyzed. The paper ends with recent developments and challenges, such as the generalization of normal ordering to arbitrary reference states, contracted Schrodinger kappa-particle equations and Brillouin conditions, and finally the Nakatsuji theorem and the Nooijen conjecture.