High-Pressure Softening of the Out-of-Plane A2u(Transverse-Optic) Mode of Hexagonal Boron Nitride Induced by Dynamical Buckling

We investigate the highly anisotropic behavior of the in-plane and out-of-plane infrared-active phonons of hexagonal boron nitride by means of infrared reflectivity and absorption measurements under high pressure. Infrared reflectivity spectra at normal incidence on high-quality single crystals show strict fulfillment of selection rules and an unusually long E1u[transverse-optic (TO)] phonon lifetime. Accurate values of the dielectric constants at ambient pressure ϵ0= 6.96, ϵ∞= 4.95, ϵ 0= 3.37, and ϵ∞ = 2.84 have been determined from fits to the reflectivity spectra. The out-of-plane A2u phonon reflectivity band is revealed in measurements on an inclined facet, and absorption measurements a…