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The Raman spectrum of plutonium dioxide is studied both experimentally and theoretically. Particular attention has been devoted to the identification of high-energy modes at 2110 and 2620 cm−1, whose attribution has so far been controversial. The temperature dependence of both modes suggests an electronic origin for them. Original crystal field (CF) calculations reported in this work show that these two modes can be respectively assigned to the 1 → 5 and 1 → 3 CF transitions within the 5I4 manifold. These two modes, together with the only vibrational line foreseen by the group theory for the Fm-3mPuO2 symmetry—the T2g Pu-O stretching mode observed at 478 cm−1—can thus be used as a Raman fingerprint of fcc plutonium dioxide.
2017-04-10
AMER PHYSICAL SOC
JRC97969
1098-0121,   
https://publications.jrc.ec.europa.eu/repository/handle/JRC97969,   
10.1103/PhysRevB.95.104307,   
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