Calculation of anharmonic OH phonon dispersion curves for the Mg(OH)2 crystal.

ABSTRACT

Anharmonic OH phonon dispersion curves have been calculated for the Mg(OH)(2) crystal. A crystal Hamiltonian was set up for the vibrational problem, where the coordinates consists of the bond lengths of two hydroxide ions in the central unit cell. Its two-dimensional potential energy surface was constructed from first principle calculations within the density functional theory approximation. Dispersion curves were calculated by diagonalizing the Hamiltonian in a basis of singly excited crystal functions. The single particle functions used to construct the crystal states were taken from a Morse oscillator basis set. These well chosen functions made it possible to restrict calculations to include only very few functions, which greatly contributed to a transparent presentation of the underlying theory. All calculations could be done analytically except for the calculation of a few integrals. We have compared our results with those of a series of harmonic lattice dynamics calculations and have found that the anharmonicity shifts the IR and Raman dispersion curves downward appreciably and slightly changes the energy differences between both curves. From an analysis of the harmonic results we conclude that incorporating the coupling between OH stretching motion and the motion of their centers of mass will appreciably change the overall features of the dispersion curves. Extension of the anharmonic model along these lines will cause no problem to the theoretical approach presented in this paper.