Anisotropic lattice thermal expansion of PbFeBO4: A study by X-ray and neutron diffraction, Raman spectroscopy and DFT calculations

• Mullite-type PbFeBO4 shows uni-axial negative coefficient of thermal expansion.
• Anisotropic thermal expansion of the metric parameters was modeled using modified Grüneisen approximation.
• The model includes harmonic, quasi-harmonic and intrinsic anharmonic contributions to the internal energy.
• DFT calculation, temperature- and pressure-dependent Raman spectra help understand the phonon decay and associated anharmonicity.

The lattice thermal expansion of mullite-type PbFeBO4 is presented in this study. The thermal expansion coefficients of the metric parameters were obtained from composite data collected from temperature-dependent neutron and X-ray powder diffraction between 10 K and 700 K. The volume thermal expansion was modeled using extended Grüneisen first-order approximation to the zero-pressure equation of state. The additive frame of the model includes harmonic, quasi-harmonic and intrinsic anharmonic potentials to describe the change of the internal energy as a function of temperature. The unit-cell volume at zero-pressure and 0 K was optimized during the DFT simulations. Harmonic frequencies of the optical Raman modes at the Γ-point of the Brillouin zone at 0 K were also calculated by DFT, which help to assign and crosscheck the experimental frequencies. The low-temperature Raman spectra showed significant anomaly in the antiferromagnetic regions, leading to softening or hardening of some phonons. Selected modes were analyzed using a modified Klemens model. The shift of the frequencies and the broadening of the line-widths helped to understand the anharmonic vibrational behaviors of the PbO4, FeO6 and BO3 polyhedra as a function of temperature.

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