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 Fe2 and Fe2− 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.
@article{arxiv.cond-mat/0608285,
title = {Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach},
author = {Heather J. Kulik and Matteo Cococcioni and Damian A. Scherlis and Nicola Marzari},
journal= {arXiv preprint arXiv:cond-mat/0608285},
year = {2009}
}