TY - JOUR
T1 - DFT + U study of uranium dioxide and plutonium dioxide with occupation matrix control
AU - Chen, Jia-li
AU - Kaltsoyannis, Nikolas
N1 - Funding Information:
We acknowledge financial support from the EPSRC (EP/T013842/1) and are grateful to The University of Manchester for access to its Computational Shared Facility and associated support services. We also thank the HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202, EP/R029431), for access to ARCHER2, the UK’s National Supercomputing Service ( https://www.archer2.ac.uk ).
Publisher Copyright:
© 2022 The Authors. Published by American Chemical Society.
PY - 2022/7/1
Y1 - 2022/7/1
N2 - DFT + U with occupation matrix control (OMC) is applied to study computationally bulk UO2 and PuO2, the latter for the first time. Using the PBESol functional in conjunction with OMC locates AFM and NM ground states for UO2 and PuO2, respectively, in agreement with experimental findings. By simulating the lattice parameter, magnetic moment, band gap, and densities of states, U = 4.0 eV is recommended for AFM UO2, yielding data close to experiments for all considered properties. U = 4.5 and 4.0 eV are recommended for NM and AFM PuO2, respectively, though much larger U values (c. 10 eV) are required to yield the most recently reported PuO2 band gap. For both oxides, several excited states have similar properties to the ground state, reinforcing the need to employ OMC wherever possible.
AB - DFT + U with occupation matrix control (OMC) is applied to study computationally bulk UO2 and PuO2, the latter for the first time. Using the PBESol functional in conjunction with OMC locates AFM and NM ground states for UO2 and PuO2, respectively, in agreement with experimental findings. By simulating the lattice parameter, magnetic moment, band gap, and densities of states, U = 4.0 eV is recommended for AFM UO2, yielding data close to experiments for all considered properties. U = 4.5 and 4.0 eV are recommended for NM and AFM PuO2, respectively, though much larger U values (c. 10 eV) are required to yield the most recently reported PuO2 band gap. For both oxides, several excited states have similar properties to the ground state, reinforcing the need to employ OMC wherever possible.
U2 - 10.1021/acs.jpcc.2c03804
DO - 10.1021/acs.jpcc.2c03804
M3 - Article
SN - 1932-7447
VL - 126
SP - 11426
EP - 11435
JO - The Journal of Physical Chemistry C
JF - The Journal of Physical Chemistry C
IS - 27
ER -