Lattice Dynamics

Abstract

Pristine graphite crystallizes according to the D46h space group. There are twelve modes of vibration associated with the three degrees of freedom of the four atoms in the primitive cell. The hexagonal Brillouin zone and the phonon dispersion curves of pristine graphite, calculated by Maeda et al. (1979), are shown in Figure 4.1. The zone-center (Γ point) modes are labeled as three acoustic modes (A2u + Elu), three infrared active modes (A2u + Elu), four Raman active modes (2E2g), and two silent modes (2Blg). The first calculation of phonon dispersion for the stage-1 compounds KC8 and RbC8 was presented by Horie et al. (1980) on the basis of the model of Maeda et al. (1979) for the lattice dynamics of pristine graphite. Although the calculated phonon energies do not agree well with the experimental data, the model has most of the ingredients for describing the lattice dynamics of stage-1 GICs. A simple review of their work is presented as follows. The primitive cell of KC8, having a p(2 × 2)R0° superlattice, contains 16 carbon atoms and two K atoms. Note that only an αβ stacking sequence is assumed here (see Section 3.6.1). The primitive translation vectors are given by t1 (0, a, 0), t2 = (−√3a/2, a/2, 0), and t3 = (−√3a/4, −a/4, c), where a = 2aG = 4.91 Å and c = 5.35 × 2 = 10.70 Å. The corresponding Brillouin zone is shown in Figure 4.2b. The phonon dispersion for KC8 has been calculated by Horie et al. (1980) on the basis of the Born-von Karman force constant model. This dispersion curve is compared with that of pristine graphite by folding the dispersion curves of graphite into the first Brillouin zone of KC8. Since the side of the Brillouin zone in KC8 is not flat in two directions, as shown in Figure 4.2b, it is a little difficult to transfer the information on the dispersion curves in the first Brillouin zone of graphite into the Brillouin zone of KC8. For simplicity, nevertheless, we assume that the side of the Brillouin zone in KC8 is flat like that of graphite.