Oxides and oxyions of the non-metals. Part XIV. Structure and reactivity of the oxyanions of transition metals. Part XIX. Electron spin resonance study of the radicals AsO42– and VO42– formed by γ-irradiation of arsenate and vanadate in calcium tungstate

Abstract

Hyperfine coupling to A for a range of X₂AO and X₃AO radicals with one electron less than the closed-shell species are reported and discussed, where X is–O^–, –OH, or–OA, and A is either metallic or nonmetalic. It is concluded that spin polarisation of the A–O σ-electrons provides the major source of spin-density on A, and that the extent of this polarisation depends strongly on the extent of p–s or d–s hybridisation for A, and weakly upon the ionic character of the ligands.