TY - JOUR
T1 - Orthogonal magnetic structures of Fe4O5
T2 - representation analysis and DFT calculations
AU - Zhandun, Vyacheslav S.
AU - Kazak, Natalia V.
AU - Kupenko, Ilya
AU - Vasiukov, Denis M.
AU - Li, Xiang
AU - Blackburn, Elizabeth
AU - Ovchinnikov, Sergei G.
PY - 2023/12/19
Y1 - 2023/12/19
N2 - The magnetic and electronic structures of Fe4O5 have been investigated at ambient and high pressures via a combination of representation analysis, density functional theory (DFT+U) calculations, and Mössbauer spectroscopy. A few spin configurations corresponding to the different irreducible representations have been considered. The total-energy calculations reveal that the magnetic ground state of Fe4O5 corresponds to an orthogonal spin order. Depending on the magnetic propagation vector k, two spin-ordered phases with minimal energy differences are realized. The lowest energy magnetic phase is related to k = (0, 0, 0) and is characterized by ferromagnetic ordering of iron magnetic moments at prismatic sites along the b-axis and antiferromagnetic ordering of iron moments at octahedral sites along the c-axis. For the k = (1/2, 0, 0) phase, the moments in the prisms are antiferromagnetically ordered along the b-axis and the moments in the octahedra are still antiferromagnetically ordered along the c-axis. Under high pressure, Fe4O5 exhibits magnetic transitions with the corresponding electronic transitions of the metal-insulator type. At a critical pressure PC ∼ 60 GPa, the Fe ions at the octahedral sites undergo a high-spin to low-spin state crossover with a decrease in the unit-cell volume of ∼4%, while the Fe ions at the prismatic sites remain in the high-spin state up to 130 GPa. This site-dependent magnetic collapse is experimentally observed in the transformation of Mössbauer spectra measured at room temperature and high pressures.
AB - The magnetic and electronic structures of Fe4O5 have been investigated at ambient and high pressures via a combination of representation analysis, density functional theory (DFT+U) calculations, and Mössbauer spectroscopy. A few spin configurations corresponding to the different irreducible representations have been considered. The total-energy calculations reveal that the magnetic ground state of Fe4O5 corresponds to an orthogonal spin order. Depending on the magnetic propagation vector k, two spin-ordered phases with minimal energy differences are realized. The lowest energy magnetic phase is related to k = (0, 0, 0) and is characterized by ferromagnetic ordering of iron magnetic moments at prismatic sites along the b-axis and antiferromagnetic ordering of iron moments at octahedral sites along the c-axis. For the k = (1/2, 0, 0) phase, the moments in the prisms are antiferromagnetically ordered along the b-axis and the moments in the octahedra are still antiferromagnetically ordered along the c-axis. Under high pressure, Fe4O5 exhibits magnetic transitions with the corresponding electronic transitions of the metal-insulator type. At a critical pressure PC ∼ 60 GPa, the Fe ions at the octahedral sites undergo a high-spin to low-spin state crossover with a decrease in the unit-cell volume of ∼4%, while the Fe ions at the prismatic sites remain in the high-spin state up to 130 GPa. This site-dependent magnetic collapse is experimentally observed in the transformation of Mössbauer spectra measured at room temperature and high pressures.
U2 - 10.1039/d3dt03437b
DO - 10.1039/d3dt03437b
M3 - Article
C2 - 38193857
AN - SCOPUS:85182388123
SN - 1477-9226
VL - 53
SP - 2242
EP - 2251
JO - Dalton Transactions
JF - Dalton Transactions
IS - 5
ER -