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Annual Review of Physical Chemistry

Volume 72, 2021

Multiconfiguration Pair-Density Functional Theory

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.

Keyword(s): correlation energy, density functional theory, electronic structure theory, molecular energetics, multiconfigurational wave function, quantum chemistry, spectroscopy
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/content/journals/10.1146/annurev-physchem-090419-043839
2021-04-20
2024-04-19
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/content/journals/10.1146/annurev-physchem-090419-043839
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Multiconfiguration Pair-Density Functional Theory
Annual Review of Physical Chemistry 72, 541 (2021); https://doi.org/10.1146/annurev-physchem-090419-043839
/content/journals/10.1146/annurev-physchem-090419-043839
/content/journals/10.1146/annurev-physchem-090419-043839
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