Formation of complex defects involving molecular oxygen by electronhyphen;hole reactions in xhyphen;irradiated KClO4and KBrO4, studied by ESR and IR spectroscopy

摘要

Complex defects of composition lsqb;XOminus;2,thinsp;O2rsqb;, X=Cl,thinsp;Br, produced by UV or xhyphen;irradiation of solid KClO4and KBrO4at 26 K are characterized by ESR and IR spectroscopy. lsqb;XOminus;2,thinsp;O2rsqb; is shown to arise during xhyphen;irradiation in a reaction between selfhyphen;trapped electrons in the form of XO2minus;4defects, and selfhyphen;trapped holes in the form of (XO4)minus;2defects. The previously described hole defect lsqb;XO2, O2rsqb; is shown to arise from oxidation of lsqb;XOminus;2, O2rsqb; by reaction with (XO4)minus;2. Thus all the abundant defects observed in xhyphen;irradiated KClO4and KBrO4stem from selfhyphen;trapping of electrons and holes and from simple reactions of the selfhyphen;trapped electrons and holes. The observed equivalence of optical excitation of the anions with electronhyphen;hole recombination may be a general property of polyatomic solids.