Surface phonons of LaB6(100): deformation of boron octahedra at the surface

The surface phonon dispersion of clean LaB₆(100) surface has been measured by means of high resolution electron energy loss spectroscopy. Eight vibrational modes, of which most are located in the energy gaps between the bulk phonon bands, have been detected. The lattice dynamical calculation of a slab-shaped crystal based on a force constant model has reproduced these experimental dispersion curves, which indicates the large increase in the force constant of interoctahedral boron-boron bond at the surface by 25%, and the large decrease in the force constants of intraoctahedral boron-boron bonds at the surface by 25–50%. These changes together with the analysis of the bulk phonon structure of metal hexaborides strongly suggest that the boron octahedra at the surface are expanded by about 0.004 nm parallel to the surface.