title: A high-resolution neutron powder diffraction investigation of galena (PbS) between 10 K and 350 K: no evidence for anomalies in the lattice parameters or atomic displacement parameters in galena or altaite (PbTe) at temperatures corresponding to the saturation of cation disorder.
abstract: The temperature dependences of the unit cell parameter and the atomic displacement parameters (adp) for galena (PbS) have been measured using high resolution neutron powder diffraction in the temperature interval 10-350 K. No evidence has been found for the anomalous behaviour recently reported in a total scattering study of galena, in which the temperature variation of both the unit cell and the adp for lead are reported to undergo a dramatic reduction at a temperature of ~250 K. The linear thermal expansion coefficient calculated from the powder diffraction study is found to be in excellent agreement with literature values over the entire temperature interval studied, and approximately 25% greater at room temperature than that determined by analysis of the pair distribution function (pdf) derived from the total scattering data. This discrepancy is shown to be attributable to a linear, temperature-dependent offset from the published temperatures in the total scattering study, and has arisen from the sample temperature being significantly lower than the experimental set point temperature. Applying this correction to the adps of the lead cation removes the anomalous temperature dependence and shows the pdf results are in agreement with the neutron powder diffraction results. Application of the identical temperature offsets to the results of the pdf analysis of data collected on altaite (PbTe) eliminates the anomalous behaviour in the unit cell and the adp for lead, bringing them in line with literature values. Contrary to the conclusions of the pdf analysis, adps for the lead cation in both galena and altaite can be described in terms of Debye-like behaviour and are consistent with the partial phonon density of states.
authors.affiliation: ISIS Facility, STFC Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire, OX11 0QX, UK. Department of Earth Sciences, The Natural History Museum, Cromwell Road, London, SW7 5BD, UK.
authors.forename: K S
authors.initials: KS
authors.lastname: Knight