Magnetic interactions and electronic structure of uvarovite and andradite garnets. An ab initio all‐electron simulation with the CRYSTAL06 program

The ground-state electronic structure of a number of magnetic phases of the garnets andradite (Ca3Fe2Si3O12) and uvarovite (Ca3Cr2Si3O12) has been investigated at the density functional theory level of approximation using the periodic ab initio code CRYSTAL. An all-electron Gaussian-type basis has been used in conjunction with the B3LYP hybrid functional. The exchange coupling constants between the first (J1a and J1b differentiating the two nonidentical sites), second (J2), and third (J3) nearest neighbors have been evaluated and are found to be in good agreement with the experimental data that is available for andradite. As a consequence of both the different J1a to J1b ratio and the opposite sign of J2 in the two minerals, different antiferromagnetic (AF) ground states are found for uvarovite and andradite, which is in agreement with experimental observation. Strong support for the additivity and transferability of the J constants is provided by calculations in which Cr and Fe ions are embedded in the related grossular structure. The mechanism for the stabilization of the AF states is discussed within the Anderson theory of superexchange; the kinetic energy gain in the AF states is calculated, and the spin density maps and profiles are examined. Density of states, charge density maps, and Mulliken population data complete the analysis of the electronic structure. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010