The photochemical and thermal decomposition of ferric oxalate

Abstract

While photoconductivity has been observed with many ionic solids, in the general case the first absorption maximum in the long wavelength end of the absorption spectrum does not correspond to the energy required to elevate an electron into the conductance band, but rather to a lower energy which is associated with the formation as an excited species called an exciton (2). This is regarded as an electron associated with its positive hole and is thus a neutral species: so despite the fact that it is mobil:: it does not contribute to the electronic conductivity of the solid. It has been found to be a kinetically significant factor in many photochemical reactions.The excited species normally returns to the ground state by a radiationless transition, i.e. by dissipating its energy thermally to the lattice. However, if the potential energy curves of the ground and excited states do not overlap then reversion to the ground state can only take place by re- emission of radiation, i.e. luminescence. Another form of fluorescence, phosphorescence, takes place if the excited species is trapped in a metastable state at an impurity centre (copper, silver or gold, in zinc sulphide) and re- emission of radiation takes place after a certain time interval, dependent on the stability of the metastable state.These phenomena represent effects of radiation which are reversible since the crystal can be restored to its ground state. In certain salts, the silver halides, metallic azides and oxalates, the effect of radiation may be permanent and result in a definite chemical change

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