Optic phonon anomalies and f-d hybridization in SmS and SmB6

The optic phonons of semiconducting SmS and of (homogeneously) mixed-valent SmS and SmB₆ have been investigated by means of Raman scattering. The dominant electron - phonon interaction upon resonantly exciting the 4f shell is revealed as a coupling of the strongly localized 4f hole at the Sm site to full symmetric (A_{j g}) displacements of the nearest neighbour anions i.e. mainly to LO(L) phonons. Semiconducting and mixed-valent, metallic SmS show a “softening” of the LO(L) phonon frequencies with respect to the other divalent and trivalent rare earth sulfides, respectively, going in parallel with a “softening” of the bulk modulus. The f-d hybridization is considered as the common origin of these phonon frequency renormalizations.