Thermodynamics of lattice vibrations in non-cubic crystals: the zinc structure revisited

A phenomenological model of anisotropic lattice vibrations is proposed, using a temperature-dependent spectral cutoff and varying Debye temperatures for the vibrational normal components. The internal lattice energy, entropy and Debye – Waller B factors of non-cubic elemental crystals are derived. The formalism developed is non-perturbative, based on temperature-dependent linear dispersion relations for the normal modes. The Debye temperatures of the vibrational normal components differ in anisotropic crystals; their temperature dependence and the varying spectral cutoff can be inferred from the experimental lattice heat capacity and B factors by least-squares regression. The zero-point internal energy of the phonons is related to the low-temperature limits of the mean-squared vibrational amplitudes of the lattice measured by X-ray and γ -ray diffraction. A specific example is discussed, the thermodynamic variables of the hexagonal close-packed zinc structure, including the temperature evolution of the B factors of zinc. In this case, the lattice vibrations are partitioned into axial and basal normal components, which admit largely differing B factors and Debye temperatures. The second-order B factors defining the non-Gaussian contribution to the Debye – Waller damping factors of zinc are obtained as well. Anharmonicity of the oscillator potential and deviations from the uniform phonon frequency distribution of the Debye theory are modeled effectively by the temperature ...

Source: Acta Crystallographica Section A - July 29, 2021 Category: Chemistry Authors: Tomaschitz, R. Tags: anisotropic lattice vibrations thermodynamic functions Debye – Waller factors non-cubic crystals temperature-dependent spectral cutoff directional Debye temperatures effective phonon speed oscillator mass heat capacity zero-point e Source Type: research