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Global Hybrid Multiconfiguration Pair-Density Functional Theory
journal contribution
posted on 2020-03-09, 18:50 authored by Mohammad Mostafanejad, Marcus Dante Liebenthal, A. Eugene DePrinceA global hybrid extension of multiconfiguration
pair-density functional
theory (MC-PDFT) is developed. Using a linear decomposition of the
electron–electron repulsion term, a fraction λ of the
nonlocal exchange interaction, obtained from variational two-electron
reduced-density matrix (v2RDM)-driven
complete active-space self-consistent field (CASSCF) theory, is combined
with its local counterpart, obtained from an on-top pair-density functional.
The resulting scheme (called λ-MC-PDFT) inherits the benefits
of MC-PDFT (e.g., its simplicity and the resolution of the symmetry
dilemma) and, when combined with the v2RDM approach to CASSCF, requires
only polynomially scaling computational effort. As a result, λ-MC-PDFT
can efficiently describe static and dynamical correlation effects
in strongly correlated systems. The efficacy of the approach is assessed
for several challenging multiconfigurational problems, including the
dissociation of molecular nitrogen, the double dissociation of a water
molecule, and the 1,3-dipolar cycloadditions of ozone to ethylene
and ozone to acetylene in the O3ADD6 benchmark set.