Low temperature thermoelastic properties of galena in a simple, self-consistent, two-term Debye model

The thermoelastic properties of the thermoelectric chalcogenide galena, lead sulfide (PbS), have been determined in the temperature interval 10–350 K from high resolution neutron powder diffraction data, and literature values of the isobaric heat capacity. Within this temperature range, galena can be described by a simple phenomenological model in which the cation and anion vibrate independently of one another in a Debye-like manner, with vibrational Debye temperatures of 120(1) K for the lead, and 324(2) K for the sulfur. Simultaneous fitting of the unit cell volume and the isochoric heat capacity to a two-term Debye internal energy function gives characteristic temperatures of 110(2), and 326(5) K in excellent agreement with the measured vibrational Debye temperatures derived from fitting the atomic displacement parameters. The thermodynamic Gruneisen constant derived from the isochoric heat capacity is found to monotonically increase with decreasing temperature, from 2.5 at 300 K, to 3.25 at 25 K, in agreement with the deductions of earlier work. The full phonon density of states calculated from the two-term Debye model shows fair agreement with that derived from density functional theory.