Soft modes and phonon interactions in Sn2P2S6 studied by neutron scattering

The low frequency lattice dynamics and its relationship to the second order paraelectric-to-ferroelectric transition in Sn2P2S6 is studied. The dispersion branches of the acoustic and lowest lying optical phonons in the a*-c* plane have been obtained in the ferroelectric phase, for z-polarized phonons. Close to the phase transition a considerable softening is found for the lowest optical mode (Px), comparable to the behaviour observed in previous Raman investigations. As found previously in Sn2P2Se6, a strong coupling between the TO(Px) and TA(uxz) phonons is observed, although, apparently, not strong enough to lead to an incommensurate phase. The soft TO(Px) mode at the zone center is observed. The temperature dependence of its frequency and damping shows that the transition is not entirely displacive. At low temperatures an unusual apparent negative LO-TO splitting is observed which is shown to arise from the coupling of the x-polarized soft mode to the nearby z-polarized optical phonon. For comparison, the soft TO(Px) dispersion in the a*-b* plane is measured in both the paraelectric and ferroelectric phases. Consistent frequency changes and LO-TO splitting are observed, revealing a significant interaction between the TA(uyx) and LA(uxx) acoustics branches and the TO and LO soft optic branches, respectively. In contrast, the nearby y-polarized optic branch shows almost no temperature dependence. Finally, the influence of piezoelectric effects on the limiting acoustic slopes in the ferroelectric phase is discussed.