Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6

Li, Nana; Fan, Fengren; Sun, Fei; Wang, Yonggang; Zhao, Yongsheng; Liu, Fengliang; Zhang, Qian; Ikuta, Daijo; Xiao, Yuming; Chow, Paul; Heald, Steve M.; Sun, Chengjun; Brewe, Dale; Li, Aiguo; Lu, Xujie; Mao, Ho-Kwang; Khomskii, Daniel I.; Wu, Hua; Yang, Wenge

doi:10.1103/PhysRevB.99.195115

Title: Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La₂FeMnO₆

Journal Article · Wed May 08 00:00:00 EDT 2019 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.99.195115· OSTI ID:1558624

Li, Nana ^[1]; Fan, Fengren ^[2]; Sun, Fei ^[1]; Wang, Yonggang ^[1]; Zhao, Yongsheng ^[1]; Liu, Fengliang ^[3]; Zhang, Qian ^[1]; Ikuta, Daijo ^[4]; Xiao, Yuming ^[4]; Chow, Paul ^[4]; Heald, Steve M. ^[5]; Sun, Chengjun ^[5]; Brewe, Dale ^[5]; Li, Aiguo ^[6]; Lu, Xujie ^[1]; Mao, Ho-Kwang ^[7]; Khomskii, Daniel I. ^[8]; Wu, Hua ^[2]; Yang, Wenge ^[1]

Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China)
Fudan Univ., Shanghai (China); Nanjing Univ., Nanjing (China)
Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Fudan Univ., Shanghai (China)
Argonne National Lab. (ANL), Argonne, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Chinese Academy of Sciences (CAS), Beijing (China)
Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China); Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
Univ. zu Köln, Köln (Germany)

Spin crossover plays a central role in the structural instability, net magnetic moment modification, metallization, and even in superconductivity in corresponding materials. Most reports on the pressure-induced spin crossover with a large volume collapse have so far focused on compounds with a single transition metal. Here we report a comprehensive high-pressure investigation of a mixed Fe-Mn perovskite La₂FeMnO₆. Under pressure, the strong coupling between Fe and Mn leads to a combined valence/spin transition: Fe³⁺(S=5/2) → Fe² + (S = 0) and Mn³⁺(S = 2) → Mn⁴⁺(S = 3/2), with an isostructural phase transition. The spin transitions of both Fe and Mn are offset by ~20 GPa of the onset pressure, and the lattice collapse occurs in between. Interestingly, Fe³⁺ ion shows an abnormal behavior when it reaches a lower valence state (Fe²⁺) accompanied by a +0.5 eV energy shift in the Fe K-absorption edge at 15 GPa. This process is associated with the charge-spin-orbital state transition from high spin Fe³⁺ to low spin Fe²⁺, caused by the significantly enhanced t_{2_g}-e_g crystal field splitting in the compressed lattice under high pressure. Density functional theory calculations confirm the energy preference of the high-pressure state with charge redistribution accompanied by spin state transition of Fe ions. Moreover, La₂FeMnO₆ maintains semiconductor behaviors even when the pressure reached 144.5 GPa as evidenced by the electrical transport measurements, despite the huge resistivity decreasing seven orders of magnitude compared with that at ambient pressure. The investigation carried out here demonstrates high flexibility of double perovskites and their good potentials for optimizing the functionality of these materials.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; NA0001974; FG02-99ER45775; FG02-94ER14466; 51527801; U1530402; 11474059; 11674064; 2016YFA0300700

OSTI ID:: 1558624

Alternate ID(s):: OSTI ID: 1511516

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Vol. 99, Issue 19; ISSN 1098-0121

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

References (57)

High-pressure phase transitions in the rare-earth orthoferrite LaFeO ₃ Etter, Martin; Müller, Melanie; Hanfland, Michael Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 70, Issue 3 https://doi.org/10.1107/S2052520614007379	journal	May 2014
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Ferromagnetic Cluster on La<sub>2</sub>FeMnO<sub>6</sub> Barrozo, Petrucio; Moreno, Nelson O.; Aguiar, José Albino Advanced Materials Research, Vol. 975 https://doi.org/10.4028/www.scientific.net/AMR.975.122	journal	July 2014
Consequences of pressure-instigated spin crossover in R FeO ₃ perovskites; a volume collapse with no symmetry modification Rozenberg, G. Kh; Pasternak, M. P.; Xu, W. M. Europhysics Letters (EPL), Vol. 71, Issue 2 https://doi.org/10.1209/epl/i2005-10071-9	journal	July 2005
Pressure-Induced High-Spin to Low-Spin Transition in FeS Evidenced by X-Ray Emission Spectroscopy Rueff, J. -P.; Kao, C. -C.; Struzhkin, V. V. Physical Review Letters, Vol. 82, Issue 16 https://doi.org/10.1103/PhysRevLett.82.3284	journal	April 1999
Similarities between structural distortions under pressure and chemical doping in superconducting BaFe2As2 Kimber, Simon A. J.; Kreyssig, Andreas; Zhang, Yu-Zhong Nature Materials, Vol. 8, Issue 6 https://doi.org/10.1038/nmat2443	journal	May 2009
Spin Crossover in Ferropericlase from First-Principles Molecular Dynamics Holmström, E.; Stixrude, L. Physical Review Letters, Vol. 114, Issue 11 https://doi.org/10.1103/PhysRevLett.114.117202	journal	March 2015
Pressure-dependent electronic structures and orbital hybridization of Mn $3 d$ states in multiferroic BiMnO $_{3}$ : A combined x-ray absorption, x-ray emission, and resonant x-ray emission study Chen, J. M.; Haw, S. C.; Lee, J. M. Physical Review B, Vol. 86, Issue 4 https://doi.org/10.1103/PhysRevB.86.045103	journal	July 2012
Charge transport properties of spin crossover systems Ruiz, Eliseo Phys. Chem. Chem. Phys., Vol. 16, Issue 1 https://doi.org/10.1039/C3CP54028F	journal	January 2014
Route to achieving giant magnetoelectric coupling in ${BaTiO}_{3} / {Sr}_{2} {CoO}_{3} F$ perovskite heterostructures Reddy, Indukuru Ramesh; Oppeneer, Peter M.; Tarafder, Kartick Physical Review B, Vol. 98, Issue 14 https://doi.org/10.1103/PhysRevB.98.140401	journal	October 2018
Spin-dependent x-ray absorption of MnO and ${MnF}_{2}$ Hämäläinen, K.; Kao, C. -C.; Hastings, J. B. Physical Review B, Vol. 46, Issue 21 https://doi.org/10.1103/PhysRevB.46.14274	journal	December 1992
Pressure effect investigations on spin-crossover coordination compounds Gaspar, Ana B.; Molnár, Gábor; Rotaru, Aurelian Comptes Rendus Chimie, Vol. 21, Issue 12 https://doi.org/10.1016/j.crci.2018.07.010	journal	December 2018
X-ray Mn $K β$ emission spectra of manganese oxides and manganates Tsutsumi, Kenjiro; Nakamori, Hiroo; Ichikawa, Kouichi Physical Review B, Vol. 13, Issue 2 https://doi.org/10.1103/PhysRevB.13.929	journal	January 1976
Finite Elastic Strain of Cubic Crystals Birch, Francis Physical Review, Vol. 71, Issue 11 https://doi.org/10.1103/PhysRev.71.809	journal	June 1947
Pressure-Induced Quenching of the Jahn-Teller Distortion and Insulator-to-Metal Transition in ${LaMnO}_{3}$ Loa, I.; Adler, P.; Grzechnik, A. Physical Review Letters, Vol. 87, Issue 12 https://doi.org/10.1103/PhysRevLett.87.125501	journal	August 2001
Spin and valence states of iron in Al-bearing silicate glass at high pressures studied by synchrotron Mossbauer and X-ray emission spectroscopy Mao, Z.; Lin, J. -F.; Yang, J. American Mineralogist, Vol. 99, Issue 2-3 https://doi.org/10.2138/am.2014.4490	journal	February 2014
Transition Metal Compounds Khomskii, Daniel I. https://doi.org/10.1017/CBO9781139096782	book	January 2014
Magnetism and the spin state in cubic perovskite $CaCo O_{3}$ synthesized under high pressure Xia, Hailiang; Dai, Jianhong; Xu, Yuanji Physical Review Materials, Vol. 1, Issue 2 https://doi.org/10.1103/PhysRevMaterials.1.024406	journal	July 2017
Spin state dependence of electrical conductivity of spin crossover materials Rotaru, Aurelian; Gural'skiy, Il'ya A.; Molnár, Gábor Chem. Commun., Vol. 48, Issue 35 https://doi.org/10.1039/C2CC30528C	journal	January 2012
Electronic Transitions in Perovskite: Possible Nonconvecting Layers in the Lower Mantle Badro, J. Science, Vol. 305, Issue 5682 https://doi.org/10.1126/science.1098840	journal	July 2004
Pressure-induced Jahn-Teller suppression and simultaneous high-spin to low-spin transition in the layered perovskite $Cs Mn F_{4}$ Aguado, Fernando; Rodriguez, Fernando; Núñez, Pedro Physical Review B, Vol. 76, Issue 9 https://doi.org/10.1103/PhysRevB.76.094417	journal	September 2007
Pressure-induced high-spin to low-spin transition in ${CaFeO}_{3}$ Takano, M.; Nasu, S.; Abe, T. Physical Review Letters, Vol. 67, Issue 23 https://doi.org/10.1103/PhysRevLett.67.3267	journal	December 1991
Spin selective x‐ray absorption spectroscopy: Demonstration using high resolution Fe K β fluorescence Peng, G.; Wang, X.; Randall, C. R. Applied Physics Letters, Vol. 65, Issue 20 https://doi.org/10.1063/1.112625	journal	November 1994
Giant thermoelectric Seebeck coefficient of a two-dimensional electron gas in SrTiO3 Ohta, Hiromichi; Kim, SungWng; Mune, Yoriko Nature Materials, Vol. 6, Issue 2 https://doi.org/10.1038/nmat1821	journal	January 2007
Complexes Derived from Strong Field Ligands. XVII. Electronic Spectra of Octahedral Nickel(II) Complexes with Ligands of the α-Diimine and Closely Related Classes Robinson, Martin A.; Curry, John D.; Busch, Daryle H. Inorganic Chemistry, Vol. 2, Issue 6 https://doi.org/10.1021/ic50010a021	journal	December 1963
Role of spin-orbit coupling in the electronic structure of $Ir O_{2}$ Das, Pranab Kumar; Sławińska, Jagoda; Vobornik, Ivana Physical Review Materials, Vol. 2, Issue 6 https://doi.org/10.1103/PhysRevMaterials.2.065001	journal	June 2018
Spin Crossover Probes Confer Multistability to Organic Conducting Polymers Koo, Yong-Sung; Galán-Mascarós, José Ramón Advanced Materials, Vol. 26, Issue 39 https://doi.org/10.1002/adma.201402579	journal	September 2014
Guest-Dependent Spin Crossover in a Nanoporous Molecular Framework Material Halder, G. J. Science, Vol. 298, Issue 5599 https://doi.org/10.1126/science.1075948	journal	November 2002
Giant Pressure-Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin-State Transition in Manganese Chalcogenides Wang, Yonggang; Bai, Ligang; Wen, Ting Angewandte Chemie, Vol. 128, Issue 35 https://doi.org/10.1002/ange.201605410	journal	July 2016
Switchable Ferroelectric Diode and Photovoltaic Effect in BiFeO ₃ Choi, T.; Lee, S.; Choi, Y. J. Science, Vol. 324, Issue 5923 https://doi.org/10.1126/science.1168636	journal	February 2009
Density-functional theory and NiO photoemission spectra Anisimov, V. I.; Solovyev, I. V.; Korotin, M. A. Physical Review B, Vol. 48, Issue 23 https://doi.org/10.1103/PhysRevB.48.16929	journal	December 1993
Reduced Radiative Conductivity of Low-Spin (Mg,Fe)O in the Lower Mantle Goncharov, A. F. Science, Vol. 312, Issue 5777 https://doi.org/10.1126/science.1125622	journal	May 2006
Epitaxial BiFeO₃ Multiferroic Thin Film Heterostructures Wang, J.; Neaton, J. B.; Zheng, H. Science, Vol. 299, Issue 5613, p. 1719-1722 https://doi.org/10.1126/science.1080615	journal	March 2003
Electrical transport, magnetism, and spin-state configurations of high-pressure phases of FeS Takele, S.; Hearne, G. R. Physical Review B, Vol. 60, Issue 7 https://doi.org/10.1103/PhysRevB.60.4401	journal	August 1999
Room-Temperature Electrical Addressing of a Bistable Spin-Crossover Molecular System Prins, Ferry; Monrabal-Capilla, María; Osorio, Edgar A. Advanced Materials, Vol. 23, Issue 13 https://doi.org/10.1002/adma.201003821	journal	February 2011
Spin equilibrium in iron(II) poly(1-pyrazolyl)borate complexes: low-temperature and high-pressure Moessbauer spectral studies Long, Gary J.; Hutchinson, Bennett B. Inorganic Chemistry, Vol. 26, Issue 4 https://doi.org/10.1021/ic00251a023	journal	February 1987
Iron Partitioning in Earth's Mantle: Toward a Deep Lower Mantle Discontinuity Badro, J. Science, Vol. 300, Issue 5620 https://doi.org/10.1126/science.1081311	journal	April 2003
Pressure Tuning of Electronic Energy Levels Drickamer, H. G. International Reviews in Physical Chemistry, Vol. 2, Issue 3 https://doi.org/10.1080/01442358209353334	journal	December 1982
Emergent superconductivity in an iron-based honeycomb lattice initiated by pressure-driven spin-crossover Wang, Yonggang; Ying, Jianjun; Zhou, Zhengyang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04326-1	journal	May 2018
First-Order Isostructural Mott Transition in Highly Compressed MnO Yoo, C. S.; Maddox, B.; Klepeis, J. -H. P. Physical Review Letters, Vol. 94, Issue 11 https://doi.org/10.1103/PhysRevLett.94.115502	journal	March 2005
Nature of the phase transition in spin crossover compounds Köhler, C. P.; Jakobi, R.; Meissner, E. Journal of Physics and Chemistry of Solids, Vol. 51, Issue 3 https://doi.org/10.1016/0022-3697(90)90052-H	journal	January 1990
Zur frage der bindungsverhältnise in komplexverbindungen des eisen(II) mit 1,10-phenanthrolin Madeja, K.; König, E. Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 4 https://doi.org/10.1016/0022-1902(63)80188-8	journal	April 1963
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Pair-distribution function and its coupling-constant average for the spin-polarized electron gas Perdew, John P.; Wang, Yue Physical Review B, Vol. 46, Issue 20 https://doi.org/10.1103/PhysRevB.46.12947	journal	November 1992
Reinvestigation of the iron-57 Moessbauer effect at high pressures in some iron(II) bis(phenanthroline) complexes Pebler, Juergen Inorganic Chemistry, Vol. 22, Issue 26 https://doi.org/10.1021/ic00168a059	journal	December 1983
Spin Crossover in a Catenane Supramolecular System Real, J. A.; Andres, E.; Munoz, M. C. Science, Vol. 268, Issue 5208 https://doi.org/10.1126/science.268.5208.265	journal	April 1995
Giant Resistance Change across the Phase Transition in Spin-Crossover Molecules Baadji, N.; Sanvito, S. Physical Review Letters, Vol. 108, Issue 21 https://doi.org/10.1103/PhysRevLett.108.217201	journal	May 2012
Magnetic Collapse in Transition Metal Oxides at High Pressure: Implications for the Earth Cohen, R. E. Science, Vol. 275, Issue 5300 https://doi.org/10.1126/science.275.5300.654	journal	January 1997
Complexes of Iron(II), Cobalt(II) and Nickel(II) with Biacetyl-bis-methylimine, 2-Pyridinal-methylimine and 2,6-Pyridindial-bis-methylimine Figgins, Paul E.; Busch, Daryle H. Journal of the American Chemical Society, Vol. 82, Issue 4 https://doi.org/10.1021/ja01489a016	journal	February 1960
Negative-pressure-induced helimagnetism in ferromagnetic cubic perovskites ${Sr}_{1 - x} {Ba}_{x} {CoO}_{3}$ Sakai, H.; Yokoyama, S.; Kuwabara, A. Physical Review Materials, Vol. 2, Issue 10 https://doi.org/10.1103/PhysRevMaterials.2.104412	journal	October 2018
Ruby, metals, and $MgO$ as alternative pressure scales: A semiempirical description of shock-wave, ultrasonic, x-ray, and thermochemical data at high temperatures and pressures Dorogokupets, Peter I.; Oganov, Artem R. Physical Review B, Vol. 75, Issue 2 https://doi.org/10.1103/PhysRevB.75.024115	journal	January 2007
Electronic structure and magnetic properties of ${LaFeO}_{3}$ at high pressure Hearne, G. R.; Pasternak, M. P.; Taylor, R. D. Physical Review B, Vol. 51, Issue 17 https://doi.org/10.1103/PhysRevB.51.11495	journal	May 1995
Spin-Transition Polymers: From Molecular Materials Toward Memory Devices Kahn, O. Science, Vol. 279, Issue 5347 https://doi.org/10.1126/science.279.5347.44	journal	January 1998
Synthesis and magnetic properties of double-perovskite oxide ${La}_{2} {MnFeO}_{6}$ thin films Yoshimatsu, K.; Nogami, K.; Watarai, K. Physical Review B, Vol. 91, Issue 5 https://doi.org/10.1103/PhysRevB.91.054421	journal	February 2015
UNUSUAL MAGNETIC PROPERTIES OF SOME SIX-COÖRDINATE COBALT(II) COMPLEXES ¹ —ELECTRONIC ISOMERS Stoufer, R. Carl; Busch, Daryle H.; Hadley, Wayne B. Journal of the American Chemical Society, Vol. 83, Issue 17 https://doi.org/10.1021/ja01478a051	journal	September 1961
High-resolution manganese x-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity Peng, G.; deGroot, F. M. F.; Haemaelaeinen, K. Journal of the American Chemical Society, Vol. 116, Issue 7 https://doi.org/10.1021/ja00086a024	journal	April 1994
Enforcing Multifunctionality: A Pressure-Induced Spin-Crossover Photomagnet Pinkowicz, Dawid; Rams, Michał; Mišek, Martin Journal of the American Chemical Society, Vol. 137, Issue 27 https://doi.org/10.1021/jacs.5b04303	journal	July 2015

Cited By (1)

B-site disorder driven multiple-magnetic phases: Griffiths phase, re-entrant cluster glass, and exchange bias in Pr ₂ CoFeO ₆ Pal, Arkadeb; Singh, Prajyoti; Gangwar, V. K. Applied Physics Letters, Vol. 114, Issue 25 https://doi.org/10.1063/1.5094905	journal	June 2019

Similar Records

Local structures of Sr{sub 2}FeMnO{sub 5+y} (y=0, 0.5) and Sr{sub 2}Fe{sub 1.5}Cr{sub 0.5}O{sub 5} from reverse Monte Carlo modeling of pair distribution function data and implications for magnetic order

Journal Article · Fri Feb 15 00:00:00 EST 2013 · Journal of Solid State Chemistry · OSTI ID:1558624

King, Graham; Ramezanipour, Farshid; Llobet, Anna; +1 more

Compressional behavior and spin state of δ-(Al,Fe)OOH at high pressures

Journal Article · Tue Sep 03 00:00:00 EDT 2019 · American Mineralogist · OSTI ID:1558624

Ohira, Itaru; Jackson, Jennifer M.; Solomatova, Natalia V.; +10 more

Electronic, magnetic and structural properties of the RFe03 antiferromagnetic-perovskites at very high pressures

Conference · Tue Jan 01 00:00:00 EST 2002 · OSTI ID:1558624

Pasternak, M; Xu, W M; Rozenberg, G Kh; +1 more

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY

Title: Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6

Citation Formats

References (57)

Cited By (1)

Similar Records

Related Subjects

Title: Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La₂FeMnO₆