Oxides and oxyions of the non-metals. Part VIII. Electron spin resonance studies of some paramagnetic chlorine oxides

Abstract

A number of paramagnetic centres, produced by irradiation of KClO₃ and KClO₄, have been studied by electron spin resonance. In KClO₃, the products of γ-irradiation at 295°k are O₃ ^–, ClO₂, and probably (ClO₂–Cl)^–. For (ClO₂–Cl)^– the principal values of the g-tensor are g_xx= 2·0021, g_yy= 2·026, and g_zz= 2·003, and those of the A-tensor are a_xx=+ 86·6, a_yy=–12, and a_zz=–9 gauss for the ³⁵Cl hyperfine interaction with the ClO₂-like fragment, and a_xx= 13·8, a_yy= 1, and a_zz= 1 gauss for the Cl^–-like fragment. Ultraviolet photolysis of ClO₂ in KClO₄(or of ClO₂ in rigid H₂SO₄) produces a centre ClOO, closely resembling the isoelectronic FOO species. In this lattice ClO₂ and ClOO are interconvertible. For ClOO the principal g-tensor values are g₁₁= 1·9983, g₂₂= 2·0017, and g₃₃= 2·0130, and those of the A-tensor are a₁₁= 5·3, a₂₂= 7·2, and a₃₃= 14·9 gauss.