TY - JOUR
T1 - Evaluating transition metal oxides within DFT-SCAN and SCAN+U frameworks for solar thermochemical applications
AU - Sai Gautam, Gopalakrishnan
AU - Carter, Emily Ann
N1 - Publisher Copyright:
© 2018 American Physical Society.
PY - 2018/9/13
Y1 - 2018/9/13
N2 - Using the strongly constrained and appropriately normed (SCAN) and SCAN+U approximations for describing electron exchange correlation (XC) within density functional theory, we investigate the oxidation energetics, lattice constants, and electronic structure of binary Ce, Mn, and Fe oxides, which are crucial ingredients for generating renewable fuels using two-step, oxide-based, solar thermochemical reactors. Unlike other common XC functionals, we find that SCAN does not overbind the O2 molecule, based on direct calculations of its bond energy and robust agreement between calculated formation enthalpies of main group oxides versus experiments. However, in the case of transition-metal oxides, SCAN systematically overestimates (i.e., yields too negative) oxidation enthalpies due to remaining self-interaction errors in the description of their ground-state electronic structure. Adding a Hubbard U term to the transition-metal centers, where the magnitude of U is determined from experimental oxidation enthalpies, significantly improves the qualitative agreement and marginally improves the quantitative agreement of SCAN+U-calculated electronic structure and lattice parameters, respectively, with experiments. Importantly, SCAN predicts the wrong ground-state structure for a few oxides, namely, Ce2O3, Mn2O3, and Fe3O4, while SCAN+U predicts the right polymorph for all systems considered in this paper. Hence, the SCAN+U framework, with an appropriately determined U, will be required to accurately describe ground-state properties and yield qualitatively consistent electronic properties for most transition-metal and rare-earth oxides.
AB - Using the strongly constrained and appropriately normed (SCAN) and SCAN+U approximations for describing electron exchange correlation (XC) within density functional theory, we investigate the oxidation energetics, lattice constants, and electronic structure of binary Ce, Mn, and Fe oxides, which are crucial ingredients for generating renewable fuels using two-step, oxide-based, solar thermochemical reactors. Unlike other common XC functionals, we find that SCAN does not overbind the O2 molecule, based on direct calculations of its bond energy and robust agreement between calculated formation enthalpies of main group oxides versus experiments. However, in the case of transition-metal oxides, SCAN systematically overestimates (i.e., yields too negative) oxidation enthalpies due to remaining self-interaction errors in the description of their ground-state electronic structure. Adding a Hubbard U term to the transition-metal centers, where the magnitude of U is determined from experimental oxidation enthalpies, significantly improves the qualitative agreement and marginally improves the quantitative agreement of SCAN+U-calculated electronic structure and lattice parameters, respectively, with experiments. Importantly, SCAN predicts the wrong ground-state structure for a few oxides, namely, Ce2O3, Mn2O3, and Fe3O4, while SCAN+U predicts the right polymorph for all systems considered in this paper. Hence, the SCAN+U framework, with an appropriately determined U, will be required to accurately describe ground-state properties and yield qualitatively consistent electronic properties for most transition-metal and rare-earth oxides.
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U2 - 10.1103/PhysRevMaterials.2.095401
DO - 10.1103/PhysRevMaterials.2.095401
M3 - Article
AN - SCOPUS:85058153537
SN - 2475-9953
VL - 2
JO - Physical Review Materials
JF - Physical Review Materials
IS - 9
M1 - 095401
ER -