Global Hybrid Multiconfiguration Pair-Density Functional Theory

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Copyright © 2020 American Chemical Society. A 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.

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ACS Applied Materials and Interfaces



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