Comparison of the high-pressure behavior of the cerium oxides Ce2O3 and CeO2

Lipp, M. J.; Jeffries, J. R.; Cynn, H.; Park Klepeis, J. -H.; Evans, W. J.; Mortensen, D. R.; Seidler, G. T.; Xiao, Y.; Chow, P.

doi:10.1103/PhysRevB.93.064106

Comparison of the high-pressure behavior of the cerium oxides $C e_{2} O_{3}$ and $Ce O_{2}$

Journal Article · Tue Feb 09 00:00:00 EST 2016 · Physical Review B

DOI:https://doi.org/10.1103/PhysRevB.93.064106· OSTI ID:1240965

Lipp, M. J. ^[1]; Jeffries, J. R. ^[1]; Cynn, H. ^[1]; Park Klepeis, J. -H. ^[1]; Evans, W. J. ^[1]; Mortensen, D. R. ^[2]; Seidler, G. T. ^[2]; Xiao, Y. ^[3]; Chow, P. ^[3]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Washington, Seattle, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

We studied the high-pressure behavior of Ce₂O₃ using angle-dispersive x-ray diffraction to 70 GPa and compared with that of CeO₂. Up to the highest pressure Ce₂O₃ remains in the hexagonal phase (space group 164, P ¯32/m1) typical for the lanthanide sesquioxides. We did not observe a theoretically predicted phase instability for 30 GPa. The isothermal bulk modulus and its pressure derivative for the quasihydrostatic case are B₀ = 111 ± 2 GPa, B'₀ = 4.7 ± 0.3, and for the case without pressure-transmitting medium B₀ = 104 ±4 GPa, B'₀ = 6.5 ± 0.4. Starting from ambient-pressure magnetic susceptibility measurements for both oxides in highly purified form,we find that the Ce atom in Ce₂O₃ behaves like a trivalent Ce³⁺ ion (2.57μB per Ce atom) in contrast to previously published data. Since x-ray emission spectroscopy of the Lγ (4d_3/2 → 2p_1/2) transition is sensitive to the 4f -electron occupancy, we also followed the high-pressure dependence of this line for both oxides up to 50 GPa. We observed no change of the respective line shape, indicating that the 4f -electron configuration is stable for both materials. We posit from this data that the 4f electrons do not drive the volume collapse of CeO₂ from the high-symmetry, low-pressure fluorite structure to the lower-symmetry orthorhombic phase.

View Accepted Manuscript (DOE)

Research Organization:: Carnegie Inst. of Washington, Argonne, IL (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC52-07NA27344; NA0001974; NA0002006; SC0002194; SC0008580

OSTI ID:: 1240965

Alternate ID(s):: OSTI ID: 1237507
OSTI ID: 1238280
OSTI ID: 1379168

Report Number(s):: LLNL-JRNL--675872

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 6 Vol. 93; ISSN 2469-9950; ISSN PRBMDO

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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