Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space

2008/01/03 by Anna I. Krylov · 1,105 citations
Engineering · Physics and Astronomy · #Advanced Chemical Physics Studies #Atomic physics #Computer science #Coupled cluster #Equations of motion #Excited state #Fock space #Formalism (music) #Ion #Ionization #Molecular Junctions and Nanostructures #Molecule #Open shell #Physics #Quantum mechanics #Space (punctuation) #Spectroscopy and Quantum Chemical Studies #Theoretical physics #Wave function

paper · doi:10.1146/annurev.physchem.59.032607.093602

published in Annual Review of Physical Chemistry 59(1), 433-462 (Annual Reviews)

openalex publication_date 2008/01/03 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/25

Abstract

The equation-of-motion coupled-cluster (EOM-CC) approach is a versatile electronic-structure tool that allows one to describe a variety of multiconfigurational wave functions within single-reference formalism. This review provides a guide to established EOM methods illustrated by examples that demonstrate the types of target states currently accessible by EOM. It focuses on applications of EOM-CC to electronically excited and open-shell species. The examples emphasize EOM's advantages for selected situations often perceived as multireference cases [e.g., interacting states of different nature, Jahn-Teller (JT) and pseudo-JT states, dense manifolds of ionized states, diradicals, and triradicals]. I also discuss limitations and caveats and offer practical solutions to some problematic situations. The review also touches on some formal aspects of the theory and important current developments.

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