Multiconfiguration Pair-Density Functional Theory

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Abstract

Kohn-Sham density functional theory with the available exchange-correlation functionals is less accurate for strongly correlated systems, which require a multiconfigurational description as a zero-order function, than for weakly correlated systems, and available functionals of the spin densities do not accurately predict energies for many strongly correlated systems when one uses multiconfigurational wave functions with spin symmetry. Furthermore, adding a correlation functional to a multiconfigurational reference energy can lead to double counting of electron correlation. Multiconfiguration pair-density functional theory (MC-PDFT) overcomes both obstacles, the second by calculating the quantum mechanical part of the electronic energy entirely by a functional, and the first by using a functional of the total density and the on-top pair density rather than the spin densities. This allows one to calculate the energy of strongly correlated systems efficiently with a pair-density functional and a suitable multiconfigurational reference function. This article reviews MC-PDFT and related background information.

Original languageEnglish (US)
Pages (from-to)541-564
Number of pages24
JournalAnnual Review of Physical Chemistry
Volume72
DOIs
StatePublished - Apr 20 2020

Bibliographical note

Funding Information:
The authors are grateful toThais Scott for help with themanuscript.Our multiconfiguration pairdensity functional theory research is supported in part by the National Science Foundation (grant CHE-1746186) and by the Air Force Office of Scientific Research (grant FA9550-16-1-0134).

Publisher Copyright:
© 2020 Annual Reviews Inc.. All rights reserved.

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