Optical and EPR investigations of the photochemistry of KCl:OH Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/b5644t76v

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  • The hydroxide ion as a substitutional defect in KC1 can be photo-dissociated at liquid nitrogen temperature by ultraviolet light. The photochemistry of this system was investigated by EPR and optical absorption methods. Theoretical calculations were also performed in an investigation of the KC1:OH system. The bleaching behavior of photochemically colored KC1:OH was studied by simultaneous visible and EPR spectroscopy, and by broad range optical spectroscopy in the range from 185 nm to 2000 nm. The behavior of the system on warming from liquid nitrogen temperature to room temperature was also studied by the same methods. Pure KC1 crystals were colored with x- or gamma-rays at room temperature and studied by EPR and optical methods. The bleaching rate of photochemically colored KC1:OH was determined to be equivalent when measured by EPR or optical data. This result contradicted data reported previously. The disappearance of the EPR spectrum of ultraviolet irradiated KC1:OH at 250 K was correlated with optical data. This showed that the disappearance of the EPR was simultaneous with the conversion of H₂O⁻ centers to F centers. Results were presented and arguments given that the products and mechanism of the bleaching of H₂0⁻ centers were analagous to the products and mechanism of bleaching F centers. Approximate quantum mechanical calculations were performed which indicated that an exchange interaction of the unpaired F and 0⁻ electrons was not responsible for the disappearance of the EPR spectrum. Suggestions were made for further investigations which may yield information on the system.
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