Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard U Approach.

H. J. KULIK, M. COCOCCIONI, D. A. SCHERLIS, N. MARZARI.

PHYSICAL REVIEW LETTERS

AMER PHYSICAL SOC

Año: 2006 vol. 97 p. 103001 - 103004

0031-9007

Transition-metal centers are the active sites for a broad variety of biological and inorganic chemicalreactions. Notwithstanding this central importance, density-functional theory calculations based ongeneralized-gradient approximations often fail to describe energetics, multiplet structures, reactionbarriers, and geometries around the active sites. We suggest here an alternative approach, derived fromthe Hubbard U correction to solid-state problems, that provides an excellent agreement with correlatedelectronquantum chemistry calculations in test cases that range from the ground state of Fe2 and Fe
2 tothe addition elimination of molecular hydrogen on FeO. The Hubbard U is determined with a novel selfconsistentprocedure based on a linear-response approach.