Lattice dynamics of solid N2 with an a b i n i t i o intermolecular potential

Abstract

We have performed harmonic and self‐consistent phonon lattice dynamics calculations for α and γ N₂ crystals using an intermolecular potential from ab initio calculations. This potential contains electrostatic (multipole) interactions, up to all R⁻⁹ terms inclusive, anisotropic dispersion interactions up to all R⁻¹⁰ terms inclusive, and anisotropic overlap interactions caused by charge penetration and exchange between the molecules. The lattice constants, cohesion energy, the frequencies of the translational phonon modes and the Grüneisen parameters for the librational modes are in good agreement with experimental values, confirming the quality of the potential. The frequencies of the librational modes and those of the mixed modes are less well reproduced, especially at temperatures near the α–β phase transition. Probably, the self‐consistent phonon method used does not fully account for the anharmonicity in the librations.