title: Simulation of heme using DFT + U: a step toward accurate spin-state energetics.
abstract: We investigate the DFT + U approach as a viable solution to describe the low-lying states of ligated and unligated iron heme complexes. Besides their central role in organometallic chemistry, these compounds represent a paradigmatic case where LDA, GGA, and common hybrid functionals fail to reproduce the experimental magnetic splittings. In particular, the imidazole pentacoordinated heme is incorrectly described as a triplet by all usual DFT flavors. In this study, we show that a U parameter close to 4 eV leads to spin transitions and molecular geometries in quantitative agreement with experiments and that DFT + U represents an appealing tool in the description of iron porphyrin complexes, at a much reduced cost compared to correlated quantum-chemistry methods. The possibility of obtaining the U parameter from first principles is explored through a self-consistent linear-response formulation. We find that this approach, which proved to be successful in other iron systems, produces in this case some overestimation with respect to the optimal values of U.
authors.affiliation: Departamento de Química InorgAnica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. II, Buenos Aires, Argentina.
authors.forename: Damian A
authors.initials: DA
authors.lastname: Scherlis
authors.forename: Matteo
authors.initials: M
authors.lastname: Cococcioni
authors.forename: Patrick
authors.initials: P
authors.lastname: Sit
authors.forename: Nicola
authors.initials: N
authors.lastname: Marzari
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D003198:Computer Simulation; D004583:Electrons; D006418:Heme / Q000737:chemistry*; D007501:Iron / Q000737:chemistry; D008024:Ligands; D008954:Models, Biological; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D008024:Ligands; D011166:Porphyrins; D006418:Heme; C107018:porphine; D002248:Carbon Monoxide; D007501:Iron; D010100:Oxygen