The algebraic diagrammatic construction scheme for the polarization propagator for the calculation of excited states

Abstract

The algebraic diagrammatic construction (ADC) scheme for the polarization propagator provides a series of ab initio methods for the calculation of excited states based on perturbation theory. In recent years, the second‐order ADC(2) scheme has attracted attention in the computational chemistry community because of its reliable accuracy and reasonable computational effort in the calculation of predominantly singly excited states. Owing to their size‐consistency, ADC methods are suited for the investigation of large molecules. In addition, their Hermitian structure and the availability of the intermediate state representation (ISR) allow for straightforward computation of excited‐state properties. Recently, an efficient implementation of ADC(3) has been reported, and its high accuracy for typical valence excited states of organic chromophores has been demonstrated. In this review, the origin of ADC‐based excited‐state methods in propagator theory is described, and an intuitive route for the derivation of algebraic expressions via the ISR is outlined and comparison to other excited‐state methods is made. Existing computer codes and implemented ADC variants are reviewed, but most importantly the accuracy and limits of different ADC schemes are critically examined. WIREs Comput Mol Sci 2015, 5:82–95. doi: 10.1002/wcms.1206This article is categorized under: Structure and Mechanism > Molecular Structures Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy