Soft modes and NTE in Zn(CN)2 from Raman spectroscopy and first principles calculations

Abstract

We have studied Zn(CN)2 at high pressure using Raman spectroscopy, and report Gruneisen parameters of the soft phonons. The phonon frequencies and eigen vectors obtained from ab-initio calculations are used for the assignment of the observed phonon spectra. Out of the eleven zone-centre optical modes, six modes exhibit negative Gruneisen parameter. The calculations suggest that the soft phonons correspond to the librational and translational modes of CN rigid unit, with librational modes contributing more to thermal expansion. A rapid disordering of the lattice is found above 1.6 GPa from X-ray diffraction.

Submitted to Phys. Rev. Letters

References in corpus (2)

• The SIESTA method for ab initio order-N materials simulation
• Efficient index handling of multidimensional periodic boundary conditions

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