Electronic structure of strongly correlated systems: recent developments in multiconfiguration pair-density functional theory and multiconfiguration nonclassical-energy functional theory

Chen Zhou, Matthew R. Hermes, Dihua Wu, Jie J. Bao, Riddhish Pandharkar, Daniel S. King, Dayou Zhang, Thais R. Scott, Aleksandr O. Lykhin, Laura Gagliardi, Donald G. Truhlar

Research output: Contribution to journalReview articlepeer-review

3 Scopus citations

Abstract

Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn-Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin-orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals.

Original languageEnglish (US)
Pages (from-to)7685-7706
Number of pages22
JournalChemical Science
Volume13
Issue number26
DOIs
StatePublished - Jun 7 2022

Bibliographical note

Funding Information:
This work was supported in part by the Air Force Office of Scientific Research (grant A9550-20-1-0360) and the National Science Foundation (grant CHE-2054723). D. Z. acknowledges partial funding from the Robert and Jill DeMaster Excellence Fellowship. T. R. S. acknowledges that this material is also based in part upon work supported by the National Science Foundation Graduate Research Fellowship Program under Grant No. CON-75851, Project No. 00074041.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

PubMed: MeSH publication types

  • Journal Article
  • Review

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