Structural and Vibrational Properties of CdAl2S4 under High Pressure: Experimental and Theoretical Approach

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• 作者：Juan 脕ngel Sans ; David Santamar铆a-P茅rez ; Catalin Popescu ; Oscar Gomis ; Francisco Javier Manj贸n ; Rosario Vilaplana ; Alfonso Mu帽oz ; Pl谩cida Rodr铆guez-Hern谩ndez ; Veaceslav V. Ursaki ; Ion M. Tiginyanu
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：July 17, 2014
• 年：2014
• 卷：118
• 期：28
• 页码：15363-15374
• 全文大小：557K
• ISSN：1932-7455

文摘

The behavior of defect chalcopyrite CdAl₂S₄ at high pressures and ambient temperature has been investigated in a joint experimental and theoretical study. High-pressure X-ray diffraction and Raman scattering measurements were complemented with theoretical ab initio calculations. The equation of state and pressure dependences of the structural parameters of CdAl₂S₄ were determined and compared to those of other AB₂X₄ ordered-vacancy compounds. The pressure dependence of the Raman-active mode frequencies is reported, as well as the theoretical phonon dispersion curves and phonon density of states at 1 atm. Our measurements suggest that defect chalcopyrite CdAl₂S₄ undergoes a phase transition above 15 GPa to a disordered-rocksalt structure, whose equation of state was also obtained up to 25 GPa. In a downstroke from 25 GPa to 1 atm, our measurements indicate that CdAl₂S₄ does not return to the defect chalcopyrite phase; it partially retains the disordered-rocksalt phase and partially transforms into the spinel structure. The nature of the spinel structure was confirmed by the good agreement of our experimental results with our theoretical calculations. All in all, our experimental and theoretical results provide evidence that the spinel and defect chalcopyrite phases of CdAl₂S₄ are competitive at 1 atm. This result opens the way to the synthesis of spinel-type CdAl₂S₄ at near-ambient conditions.