TY - JOUR
T1 - Structure and Properties of Cubic PuH2 and PuH3
T2 - A Density Functional Theory Study
AU - Smith, Thomas
AU - Moxon, Samuel
AU - Cooke, David J.
AU - Gillie, Lisa J.
AU - Harker, Robert M.
AU - Storr, Mark T.
AU - Da silva, Estelina Lora
AU - Molinari, Marco
N1 - Funding Information:
We would like to acknowledge the EPSRC DTP 2018-19 University of Huddersfield (EP/R513234/1). Analysis was performed on the Orion computing facility at the University of Huddersfield. Calculations were run on the ARCHER and ARCHER2 UK National Supercomputing Services via our membership of the UK HEC Materials Chemistry Consortium (MCC; EPSRC EP/L000202, EP/R029431). EldS acknowledges the Network of Extreme Conditions Laboratories (NECL), financed by FCT and co-financed by NORTE 2020, through the programme Portugal 2020 and FEDER. To the extent that this paper relies on the contribution of RMH/MTS, then the copyright vests in the @British Crown Copyright 2020/AWE.
Publisher Copyright:
© 2022 by the authors.
PY - 2022/10/21
Y1 - 2022/10/21
N2 - The presence of cubic PuH2 and PuH3, the products of hydrogen corrosion of Pu, during long-term storage is of concern because of the materials’ pyrophoricity and ability to catalyse the oxidation reaction of Pu to form PuO2. Here, we modelled cubic PuH2 and PuH3 using Density Functional Theory (DFT) and assessed the performance of the PBEsol+U+SOC (0 ≤ U ≤ 7 eV) including van der Waals dispersion using the Grimme D3 method and the hybrid HSE06sol+SOC. We investigated the structural, magnetic and electronic properties of the cubic hydride phases. We considered spin–orbit coupling (SOC) and non-collinear magnetism to study ferromagnetic (FM), longitudinal and transverse antiferromagnetic (AFM) orders aligned in the , and directions. The hybrid DFT confirmed that FM orders in the and directions were the most stable for cubic PuH2 and PuH3, respectively. For the standard DFT, the most stable magnetic order is dependent on the value of U used, with transitions in the magnetic order at higher U values (U > 5 eV) seen for both PuH2 and PuH3.
AB - The presence of cubic PuH2 and PuH3, the products of hydrogen corrosion of Pu, during long-term storage is of concern because of the materials’ pyrophoricity and ability to catalyse the oxidation reaction of Pu to form PuO2. Here, we modelled cubic PuH2 and PuH3 using Density Functional Theory (DFT) and assessed the performance of the PBEsol+U+SOC (0 ≤ U ≤ 7 eV) including van der Waals dispersion using the Grimme D3 method and the hybrid HSE06sol+SOC. We investigated the structural, magnetic and electronic properties of the cubic hydride phases. We considered spin–orbit coupling (SOC) and non-collinear magnetism to study ferromagnetic (FM), longitudinal and transverse antiferromagnetic (AFM) orders aligned in the , and directions. The hybrid DFT confirmed that FM orders in the and directions were the most stable for cubic PuH2 and PuH3, respectively. For the standard DFT, the most stable magnetic order is dependent on the value of U used, with transitions in the magnetic order at higher U values (U > 5 eV) seen for both PuH2 and PuH3.
KW - plutonium hydrides
KW - structural properties
KW - magnetic properties
KW - electronic properties
KW - hybrid density functional theory
UR - http://www.scopus.com/inward/record.url?scp=85140907411&partnerID=8YFLogxK
U2 - 10.3390/cryst12101499
DO - 10.3390/cryst12101499
M3 - Article
VL - 12
JO - Crystals
JF - Crystals
SN - 2073-4352
IS - 10
M1 - 1499
ER -
