Abstract

We present an experimental study of the high-pressure, high-temperature behaviour of cerium up to ∼22 GPa and 820 K using angle-dispersive x-ray diffraction and external resistive heating. Studies above 820 K were prevented by chemical reactions between the samples and the diamond anvils of the pressure cells. We unambiguously measure the stability region of the orthorhombic oC4 phase and find it reaches its apex at 7.1 GPa and 650 K. We locate the α-cF4–oC4–tI2 triple point at 6.1 GPa and 640 K, 1 GPa below the location of the apex of the oC4 phase, and 1–2 GPa lower than previously reported. We find the α-cF4 → tI2 phase boundary to have a positive gradient of 280 K (GPa)−1, less steep than the 670 K (GPa)−1 reported previously, and find the oC4 → tI2 phase boundary to lie at higher temperatures than previously found. We also find variations as large as 2–3 GPa in the transition pressures at which the oC4 → tI2 transition takes place at a given temperature, the reasons for which remain unclear. Finally, we find no evidence that the α-cF4 → tI2 is not second order at all temperatures up to 820 K.

Highlights

  • Cerium (Ce) has long been the focus of both computational and experimental studies of 4f electron behaviour, and is a perfect example of an element displaying a pressureinduced electronic transition [1]

  • We find the α-cF 4 → tI 2 phase boundary to have a positive gradient of 280 K/GPa, less steep than the 670 K/GPa reported previously, and find the oC 4 → tI 2 phase boundary to lie at higher temperatures than previously found

  • Angle dispersive x-ray powder diffraction experiments have been performed on Ce up to 22 GPa and 820 K, with the aim of determining the stability region of the oC 4 phase, and nature of the α-cF 4 → tI 2 phase boundary

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Summary

Introduction

Cerium (Ce) has long been the focus of both computational and experimental studies of 4f electron behaviour, and is a perfect example of an element displaying a pressureinduced electronic transition [1]. This uncertainty is further highlighted by our own preliminary diffraction data obtained on isothermal compression at ∼650 K, which showed a α-cF 4 → tI 2 → oC 4 → tI 2 transition sequence

Experimental Details
Room-Temperature Compression
Resistive-Heating Studies
Conclusions
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