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Vibrational and thermodynamic properties of Ni3S2 polymorphs from first-principles calculations

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Abstract

We have calculated the compressional, vibrational, and thermodynamic properties of Ni3S2 heazlewoodite and the high-pressure orthorhombic phase (with Cmcm symmetry) using the generalized gradient approximation to the density functional theory in conjunction with the quasi-harmonic approximation. The predicted Raman frequencies of heazlewoodite are in good agreement with room-temperature measurements. The calculated thermodynamic properties of heazlewoodite at room conditions agree very well with experiments, but at high temperatures (especially above 500 K) the heat capacity data from experiments are significantly larger than the quasi-harmonic results, indicating that heazlewoodite is anharmonic. On the other hand, the obtained vibrational density of states of the orthorhombic phase at 20 GPa reveals a group of low-frequency vibrational modes which are absent in heazlewoodite. These low-frequency modes contribute substantially to thermal expansivity, heat capacity, entropy, and Grüneisen parameter of the orthorhombic phase. The calculated phase boundary between heazlewoodite and the orthorhombic phase is consistent with high-pressure experiments; the predicted transition pressure is 17.9 GPa at 300 K with a negative Clapeyron slope of −8.5 MPa/K.

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Acknowledgments

Research supported by NSF grant EAR-0609885 to N. L. Ross, G. V. Gibbs and R. J. Angel. Computations are performed on the Hess cluster at the Geoscicence Department at Virginia Tech. YGY appreciates Prof. S. King and Prof. Y. Zhou for kindly sharing their computational resources and thanks R. Godbee for technical support.

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  1. Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA, 24060, USA

    Yonggang G. Yu & Nancy L. Ross

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  1. Yonggang G. Yu
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  2. Nancy L. Ross
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Correspondence to Yonggang G. Yu.

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Yu, Y.G., Ross, N.L. Vibrational and thermodynamic properties of Ni3S2 polymorphs from first-principles calculations. Phys Chem Minerals 38, 241–249 (2011). https://doi.org/10.1007/s00269-010-0399-7

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