Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach

Abstract

Transition-metal centers are the active sites for many biological and inorganic chemical reactions. Notwithstanding this central importance, density-functional theory calculations based on generalized-gradient approximations often fail to describe energetics, multiplet structures, reaction barriers, and geometries around the active sites. We suggest here an alternative approach, derived from the Hubbard U correction to solid-state problems, that provides an excellent agreement with correlated-electron quantum chemistry calculations in test cases that range from the ground state of Fe${}_2$ and Fe${}_2^{-}$ to the addition-elimination of molecular hydrogen on FeO${}^{+}$. The Hubbard U is determined with a novel self-consistent procedure based on a linear-response approach.

5 pages, 3 figures, Phys. Rev. Lett., in press

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