Colour due to Cr3+ ions in oxides: a study of the model system MgO:Cr3+.

Seeking to understand why the cubic centre in MgO:Cr(3+) has the same 10Dq value as emerald, ab initio cluster and periodic supercell calculations have been performed. It is found that the equilibrium Cr(3+)-O(2-) distance, R, in MgO:Cr(3+) is equal to 2.03 Å and thus 0.06 Å higher than that measured for the emerald. Calculations carried out on the isolated CrO(6)(9-) complex at R = 2.03 Å give 10Dq = 14,510 cm(-1), which is 10% smaller than the experimental figure for MgO:Cr(3+). Nevertheless, when the internal electric field, ER(r), due to the rest of the lattice ions is also taken into account, the calculated 10Dq = 16,210 cm(-1) coincides with the experimental value. Accordingly, the colour shift for different oxides doped with Cr(3+) can be well understood on the basis of this extrinsic contribution to 10Dq usually ignored in a ligand field description. The calculated electrostatic potential, VR(r), related to ER(r), is found to be attractive when the electronic density is lying along <110> directions and |r| > 1 Å driven by the first shell of twelve Mg(2+) ions. The action of VR(r) upon the CrO(6)(9-) complex slightly decreases the energy of t2g(xy,xz,yz) orbitals with respect to that for eg(3z(2) - r(2),x(2) - y(2)) orbitals, thus enhancing the 10Dq value by 0.2 eV. However, the addition of VR(r) induces very small changes in the electronic density, a relevant fact that is related to the (2)E(t(2g)(3)) −> (4)A(2)(t(2g)(3)) emission energy being nearly independent of the host lattice along the series of Cr(3+)-doped oxides.