  The formalism of electronic density-functional-theory, with Hubbard-U
corrections (DFT+U), is employed in a computational study of the energetics of
U_{1-x} Ce_x O_2 mixtures. The computational approach makes use of a procedure
which facilitates convergence of the calculations to multiple self-consistent
DFT+U solutions for a given cation arrangement, corresponding to different
charge states for the U and Ce ions in several prototypical cation
arrangements. Results indicate a significant dependence of the structural and
energetic properties on the nature of both charge and cation ordering. With the
effective Hubbard-U parameters that reproduce well the measured
oxidation-reduction energies for urania and ceria, we find that charge transfer
between U(IV) and Ce(IV) ions, leading to the formation of U(V) and Ce(III),
gives rise to an increase in the mixing energy in the range of 4-14 kJ/mol of
formula unit, depending on the nature of the cation ordering. The results
suggest that although charge transfer between uranium and cerium ions is
disfavored energetically, it is likely to be entropically stabilized at the
high temperatures relevant to the processing and service of urania-based solid
solutions.
