Details

Autor(en) / Beteiligte

• Vélez, Ederley
• Alberola, Antonio
• Polo, Víctor

Titel

A Density Functional Theory Study of the Magnetic Exchange Coupling in Dinuclear Manganese(II) Inverse Crown Structures

Ist Teil von

• The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2009-12, Vol.113 (50), p.14008-14013

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2009

Quelle

MEDLINE

Beschreibungen/Notizen

• The magnetic exchange coupling constants between two Mn(II) centers for a set of five inverse crown structures have been investigated by means of a methodology based on broken-symmetry unrestricted density functional theory. These novel and highly unstable compounds present superexchange interactions between two Mn centers, each one with S = 5/2 through anionic “guests” such as oxygen, benzene, or hydrides or through the cationic ring formed by amide ligands and alkali metals (Na, Li). Magnetic exchange couplings calculated at B3LYP/6-31G(d,p) level yield strong antiferromagnetic couplings for compounds linked via an oxygen atom or hydride and very small antiferromagnetic couplings for those linked via a benzene molecule, deprotonated in either 1,4- or 1,3- positions. Analysis of the magnetic orbitals and spin polarization maps provide an understanding of the exchange mechanism between the Mn centers. The dependence of J with respect to 10 different density functional theory potentials employed and the basis set has been analyzed.