Dependence of Van-Vleck paramagnetism on the size of nanocrystals in superstoichiometric TiOy

Resumo

In situ measurements of the magnetic susceptibility of titanium monoxide nanocrystals with superstoichiometric composition TiO_y (y > 1) in the 300–1200 K temperature range showed that this value depends not only on the structural state of a sample, but also on the size of crystals. Analysis of data obtained for both ordered and disordered TiO_y showed that the Van-Vleck paramagnetism is inversely proportional to the nanocrystal size because of breakage of the symmetry of local environment of the near-surface atoms of titanium and oxygen. The Van-Vleck paramagnetism contribution due to atomic-vacancy disorder in superstoichiometric titanium monoxide nanocrystals, as well as in the stoichiometric composition, is proportional to a deviation of the degree of long-range order from its maximum value.