Oxides and oxyions of the non-metals. Part VIII. Electron spin resonance studies of some paramagnetic chlorine oxides
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 gxx= 2·0021, gyy= 2·026, and gzz= 2·003, and those of the A-tensor are axx=+ 86·6, ayy=–12, and azz=–9 gauss for the 35Cl hyperfine interaction with the ClO2-like fragment, and axx= 13·8, ayy= 1, and azz= 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.