Electron spin resonance g tensors for complexes of Ne and Ar with AlO: Theoretical studies related to the large matrix effect observed for AlO

For Nen–AlO (n=2, 4, 6, 8, 10) and Arn–AlO clusters (n=2, 4, 6, 8), the perpendicular (relative to AlO) component of the g tensor was calculated by second-order perturbation theory, using multireference configuration-interaction wave functions. The rare-gas (Rg) atoms were placed axially and/or off axially (one or two rings of four Rg atoms each), and the distance of the Rg atoms from the Al and O atoms, or from the AlO axis, was varied from 4 to 12 bohrs. Rg atoms placed axially mostly increase g⊥, whereas off-axially placed ones lower it below the gas-phase value of AlO. The largest deviations from g⊥ of isolated AlO occur at Ne–Al,O distances of 5–6 bohrs, and Ar–Al,O distances of 6–9 bohrs, with maximal lowerings of about 1600 ppm for Ne and about 2200 ppm (estimated) for Ar in the case of two axial and eight off-axial Rg atoms. Electron spin resonance studies by Knight and Weltner found large matrix effects for AlO, with downshifts of g⊥ observed to be about 450 and 1150 ppm in Ne and Ar matrices, respectively.