Publications

Lattice dynamics and thermomechanical properties of zirconium(IV) chloride: Evidence for low-temperature negative thermal expansion

Kim, Eunja; Weck, Philippe F.; Borjas, Rosendo; Poineau, Frederic

The crystal structure, lattice dynamics and themomechanical properties of bulk monoclinic zirconium tetrachloride (ZrCl4) have been investigated using zero-damping dispersion-corrected density functional theory [DFT-D3(zero)]. Phonon analysis reveals that ZrCl4(cr) undergoes negative thermal expansion (NTE) near T≈10 K, with a coefficient of thermal expansion of α=-1.2 ppm K−1 and a Grüneisen parameter of γ=-1.1. The bulk modulus is predicted to vary from K0=8.7 to 7.0 GPa in the temperature range 0–550 K. The isobaric molar heat capacity derived from phonon calculations within the quasi-harmonic approximation is in fair agreement with existing calorimetric data.