The self-trapped hole in caesium halides

Abstract

The equilibrium lattice configuration, electronic excitation energies and activation energies for hopping motion are calculated for a self-trapped hole in simple cubic CsCl, CsBr and CsI. The defect is regarded as a X2- molecular ion (X=Cl, Br, I) whose bond-length has been modified by the crystalline environment. Agreement with the experimental ultraviolet transition energies is good. Excitation energies deduced from measurement of g-shifts in CsBr and CsI are too low, a feature common to all alkali bromides and iodides, and attributed to the approximations involved in their deviation. The initial calculations predict lower activation energies of 90 degrees jumps than for 180 degrees jumps, in contrast with what is observed in CsI. An alternative model is presented, which reproduces the correct trend. Comparison of the actual numbers with experiment is hampered by the fact that the latter are done at low temperature (60-90K), the calculations being done in the high-temperature limit.