  Phonon density of states (PDOS) measurements have been performed on
polycrystalline UO2 at 295 and 1200 K using time-of-flight inelastic neutron
scattering to investigate the impact of anharmonicity on the vibrational
spectra and to benchmark ab initio PDOS simulations performed on this strongly
correlated Mott-insulator. Time-of-flight PDOS measurements include anharmonic
linewidth broadening inherently and the factor of ~ 7 enhancement of the oxygen
spectrum relative to the uranium component by the neutron weighting increases
sensitivity to the oxygen-dominated optical phonon modes. The first-principles
simulations of quasi-harmonic PDOS spectra were neutron-weighted and
anharmonicity was introduced in an approximate way by convolution with
wavevector-weighted averages over our previously measured phonon linewidths for
UO2 that are provided in numerical form. Comparisons between the PDOS
measurements and the simulations show reasonable agreement overall, but they
also reveal important areas of disagreement for both high and low temperatures.
The discrepancies stem largely from an ~ 10 meV compression in the overall
bandwidth (energy range) of the oxygen-dominated optical phonons in the
simulations. A similar linewidth-convoluted comparison performed with the PDOS
spectrum of Dolling et al. obtained by shell-model fitting to their historical
phonon dispersion measurements shows excellent agreement with the
time-of-flight PDOS measurements reported here. In contrast, we show by
comparisons of spectra in linewidth-convoluted form that recent
first-principles simulations for UO2 fail to account for the PDOS spectrum
determined from the measurements of Dolling et al. These results demonstrate
PDOS measurements to be stringent tests for ab initio simulations of phonon
physics in UO2 and they indicate further the need for advances in theory to
address lattice dynamics of UO2.
