Multireference Perturbation Theories Based on the Dyall Hamiltonian

TL;DR

This review discusses two multireference perturbation theories based on the Dyall Hamiltonian, highlighting their theoretical foundations, relationships, and potential for treating static and dynamic correlation in molecules.

Contribution

It provides a comprehensive overview of two approaches—N-electron valence perturbation theory and multireference algebraic diagrammatic construction—based on the Dyall Hamiltonian, including technical details and future outlook.

Findings

Clarifies the relationship between the two theories.

Summarizes alternative approaches using the Dyall Hamiltonian.

Outlines future directions for development.

Abstract

The concept of Dyall zeroth-order Hamiltonian [Dyall, K. G. J. Chem. Phys., 102, 4909-4918 (1995)] has been instrumental in the development of intruder- and parameter-free multireference perturbation theories for the efficient treatment of static and dynamic correlation in molecular systems. In this review, we discuss two theoretical approaches based on the Dyall Hamiltonian: (i) N-electron valence perturbation theory and (ii) multireference algebraic diagrammatic construction theory. We briefly cover the technical aspects behind these theories and discuss their relationship. We conclude with a short description of alternative approaches based on the Dyall Hamiltonian, a summary, and an outlook on future developments.