Structural phase transition and internal fields in rubidium thiocyanate probed through vibrational spectroscopy

A comprehensive vibrational study of Rubidium thiocyanate (RbNCS), in the 298–448°K range reveals that the orthorhombic to tetragonal transition atT _c440°K is of order-disorder type exhibiting purely second order characteristics. A consistent order-parameter exponent 0.45±0.04 has been obtained from both Raman and IR measurements. In the Raman spectra, the appearance of sidebands in both the C–N&C–S stretching modes and their temperature dependence indicate the existence and a gradual diminution of internal electric field asT approachesT _c. These results have been discussed in the context of an anharmonic oscillator model. An activation energy (U) for the reorientational motion of NCS^– ions,U0.29±0.02 eV, has been calculated from large changes in the bandwidth (_C-N) nearT _c.