Magnetic Exchange Couplings with Range-Separated Hybrid Functionals

JUAN E. PERALTA; J. I. MELO

JOURNAL OF CHEMICAL THEORY AND COMPUTATION

AMER CHEMICAL SOC

Lugar: Washington, DC; Año: 2010 p. 1894 - 1899

1549-9618

We investigate the effect of Hartree-Fock range-separation on the calculation of magnetic exchange couplings in a set of nine bi-metallic transition-metal complexes containing 3d elements (V, Cr, Mn and Cu). To this end, we have compared magnetic exchange couplings calculated as self-consistent energy differences using two global hybrid functionals, B3LYP (Becke 3-parameter exchange and Lee-Yang-Parr correlation) and PBEh (hybrid Perdew-Burke-Ernzerhof) with the short-range separated HSE (Heyd-Scuseria-Ernzerhof) and the long-range corrected LC-ω PBE. Our results show that, although there is no clear superiority of any of these func-tionals when comparing with experimental data, the LC-ω PBE provides a better description of the magnetization on the metallic centers, yielding self-consistent solutions that mimic more closely a Heisenberg-like behavior.