Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La 2FeMnO 6
Abstract
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 La 2FeMnO 6. Under pressure, the strong coupling between Fe and Mn leads to a combined valence/spin transition: Fe 3+(S=5/2) → Fe 2 + (S = 0) and Mn 3+(S = 2) → Mn 4+(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, Fe 3+ ion shows an abnormal behavior when it reaches a lower valence state (Fe 2+) 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 Fe 3+ to low spin Fe 2+, caused by the significantly enhanced t2g-eg crystal field splitting in the compressed lattice under high pressure. Density functional theory calculations confirm the energy preference of themore »
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Science Foundation (NSF); USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1558624
- Alternate Identifier(s):
- OSTI ID: 1511516
- Grant/Contract Number:
- AC02-06CH11357; NA0001974; FG02-99ER45775; FG02-94ER14466; 51527801; U1530402; 11474059; 11674064; 2016YFA0300700
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Physical Review. B, Condensed Matter and Materials Physics
- Additional Journal Information:
- Journal Volume: 99; Journal Issue: 19; Journal ID: ISSN 1098-0121
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
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, and Yang, Wenge. Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6. United States: N. p., 2019.
Web. doi:10.1103/PhysRevB.99.195115.
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. Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6. United States. https://doi.org/10.1103/PhysRevB.99.195115
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, and Yang, Wenge. Wed .
"Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6". United States. https://doi.org/10.1103/PhysRevB.99.195115. https://www.osti.gov/servlets/purl/1558624.
@article{osti_1558624,
title = {Pressure-enhanced interplay between lattice, spin, and charge in the mixed perovskite La2FeMnO6},
author = {Li, Nana and Fan, Fengren and Sun, Fei and Wang, Yonggang and Zhao, Yongsheng and Liu, Fengliang and Zhang, Qian and Ikuta, Daijo and Xiao, Yuming and Chow, Paul and Heald, Steve M. and Sun, Chengjun and Brewe, Dale and Li, Aiguo and Lu, Xujie and Mao, Ho-Kwang and Khomskii, Daniel I. and Wu, Hua and Yang, Wenge},
abstractNote = {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 t2g-eg 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.},
doi = {10.1103/PhysRevB.99.195115},
url = {https://www.osti.gov/biblio/1558624},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
issn = {1098-0121},
number = 19,
volume = 99,
place = {United States},
year = {2019},
month = {5}
}
Web of Science
Works referenced in this record:
High-pressure phase transitions in the rare-earth orthoferrite LaFeO 3
journal, May 2014
- Etter, Martin; Müller, Melanie; Hanfland, Michael
- Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 70, Issue 3
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Ferromagnetic Cluster on La<sub>2</sub>FeMnO<sub>6</sub>
journal, July 2014
- Barrozo, Petrucio; Moreno, Nelson O.; Aguiar, José Albino
- Advanced Materials Research, Vol. 975
Consequences of pressure-instigated spin crossover in R FeO 3 perovskites; a volume collapse with no symmetry modification
journal, July 2005
- Rozenberg, G. Kh; Pasternak, M. P.; Xu, W. M.
- Europhysics Letters (EPL), Vol. 71, Issue 2
Pressure-Induced High-Spin to Low-Spin Transition in FeS Evidenced by X-Ray Emission Spectroscopy
journal, April 1999
- Rueff, J. -P.; Kao, C. -C.; Struzhkin, V. V.
- Physical Review Letters, Vol. 82, Issue 16
Similarities between structural distortions under pressure and chemical doping in superconducting BaFe2As2
journal, May 2009
- Kimber, Simon A. J.; Kreyssig, Andreas; Zhang, Yu-Zhong
- Nature Materials, Vol. 8, Issue 6
Spin Crossover in Ferropericlase from First-Principles Molecular Dynamics
journal, March 2015
- Holmström, E.; Stixrude, L.
- Physical Review Letters, Vol. 114, Issue 11
Pressure-dependent electronic structures and orbital hybridization of Mn states in multiferroic BiMnO : A combined x-ray absorption, x-ray emission, and resonant x-ray emission study
journal, July 2012
- Chen, J. M.; Haw, S. C.; Lee, J. M.
- Physical Review B, Vol. 86, Issue 4
Charge transport properties of spin crossover systems
journal, January 2014
- Ruiz, Eliseo
- Phys. Chem. Chem. Phys., Vol. 16, Issue 1
Route to achieving giant magnetoelectric coupling in perovskite heterostructures
journal, October 2018
- Reddy, Indukuru Ramesh; Oppeneer, Peter M.; Tarafder, Kartick
- Physical Review B, Vol. 98, Issue 14
Spin-dependent x-ray absorption of MnO and
journal, December 1992
- Hämäläinen, K.; Kao, C. -C.; Hastings, J. B.
- Physical Review B, Vol. 46, Issue 21
Pressure effect investigations on spin-crossover coordination compounds
journal, December 2018
- Gaspar, Ana B.; Molnár, Gábor; Rotaru, Aurelian
- Comptes Rendus Chimie, Vol. 21, Issue 12
X-ray Mn emission spectra of manganese oxides and manganates
journal, January 1976
- Tsutsumi, Kenjiro; Nakamori, Hiroo; Ichikawa, Kouichi
- Physical Review B, Vol. 13, Issue 2
Finite Elastic Strain of Cubic Crystals
journal, June 1947
- Birch, Francis
- Physical Review, Vol. 71, Issue 11
Pressure-Induced Quenching of the Jahn-Teller Distortion and Insulator-to-Metal Transition in
journal, August 2001
- Loa, I.; Adler, P.; Grzechnik, A.
- Physical Review Letters, Vol. 87, Issue 12
Spin and valence states of iron in Al-bearing silicate glass at high pressures studied by synchrotron Mossbauer and X-ray emission spectroscopy
journal, February 2014
- Mao, Z.; Lin, J. -F.; Yang, J.
- American Mineralogist, Vol. 99, Issue 2-3
Magnetism and the spin state in cubic perovskite synthesized under high pressure
journal, July 2017
- Xia, Hailiang; Dai, Jianhong; Xu, Yuanji
- Physical Review Materials, Vol. 1, Issue 2
Spin state dependence of electrical conductivity of spin crossover materials
journal, January 2012
- Rotaru, Aurelian; Gural'skiy, Il'ya A.; Molnár, Gábor
- Chem. Commun., Vol. 48, Issue 35
Electronic Transitions in Perovskite: Possible Nonconvecting Layers in the Lower Mantle
journal, July 2004
- Badro, J.
- Science, Vol. 305, Issue 5682
Pressure-induced Jahn-Teller suppression and simultaneous high-spin to low-spin transition in the layered perovskite
journal, September 2007
- Aguado, Fernando; Rodriguez, Fernando; Núñez, Pedro
- Physical Review B, Vol. 76, Issue 9
Pressure-induced high-spin to low-spin transition in
journal, December 1991
- Takano, M.; Nasu, S.; Abe, T.
- Physical Review Letters, Vol. 67, Issue 23
Spin selective x‐ray absorption spectroscopy: Demonstration using high resolution Fe K β fluorescence
journal, November 1994
- Peng, G.; Wang, X.; Randall, C. R.
- Applied Physics Letters, Vol. 65, Issue 20
Giant thermoelectric Seebeck coefficient of a two-dimensional electron gas in SrTiO3
journal, January 2007
- Ohta, Hiromichi; Kim, SungWng; Mune, Yoriko
- Nature Materials, Vol. 6, Issue 2
Complexes Derived from Strong Field Ligands. XVII. Electronic Spectra of Octahedral Nickel(II) Complexes with Ligands of the α-Diimine and Closely Related Classes
journal, December 1963
- Robinson, Martin A.; Curry, John D.; Busch, Daryle H.
- Inorganic Chemistry, Vol. 2, Issue 6
Role of spin-orbit coupling in the electronic structure of
journal, June 2018
- Das, Pranab Kumar; Sławińska, Jagoda; Vobornik, Ivana
- Physical Review Materials, Vol. 2, Issue 6
Spin Crossover Probes Confer Multistability to Organic Conducting Polymers
journal, September 2014
- Koo, Yong-Sung; Galán-Mascarós, José Ramón
- Advanced Materials, Vol. 26, Issue 39
Guest-Dependent Spin Crossover in a Nanoporous Molecular Framework Material
journal, November 2002
- Halder, G. J.
- Science, Vol. 298, Issue 5599
Giant Pressure-Driven Lattice Collapse Coupled with Intermetallic Bonding and Spin-State Transition in Manganese Chalcogenides
journal, July 2016
- Wang, Yonggang; Bai, Ligang; Wen, Ting
- Angewandte Chemie, Vol. 128, Issue 35
Switchable Ferroelectric Diode and Photovoltaic Effect in BiFeO 3
journal, February 2009
- Choi, T.; Lee, S.; Choi, Y. J.
- Science, Vol. 324, Issue 5923
Density-functional theory and NiO photoemission spectra
journal, December 1993
- Anisimov, V. I.; Solovyev, I. V.; Korotin, M. A.
- Physical Review B, Vol. 48, Issue 23
Reduced Radiative Conductivity of Low-Spin (Mg,Fe)O in the Lower Mantle
journal, May 2006
- Goncharov, A. F.
- Science, Vol. 312, Issue 5777
Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures
journal, March 2003
- Wang, J.; Neaton, J. B.; Zheng, H.
- Science, Vol. 299, Issue 5613, p. 1719-1722
Role of entropy and structural parameters in the spin-state transition of
journal, November 2017
- Chakrabarti, Bismayan; Birol, Turan; Haule, Kristjan
- Physical Review Materials, Vol. 1, Issue 6
Electrical transport, magnetism, and spin-state configurations of high-pressure phases of FeS
journal, August 1999
- Takele, S.; Hearne, G. R.
- Physical Review B, Vol. 60, Issue 7
Room-Temperature Electrical Addressing of a Bistable Spin-Crossover Molecular System
journal, February 2011
- Prins, Ferry; Monrabal-Capilla, María; Osorio, Edgar A.
- Advanced Materials, Vol. 23, Issue 13
Spin equilibrium in iron(II) poly(1-pyrazolyl)borate complexes: low-temperature and high-pressure Moessbauer spectral studies
journal, February 1987
- Long, Gary J.; Hutchinson, Bennett B.
- Inorganic Chemistry, Vol. 26, Issue 4
Iron Partitioning in Earth's Mantle: Toward a Deep Lower Mantle Discontinuity
journal, April 2003
- Badro, J.
- Science, Vol. 300, Issue 5620
Pressure-induced breakdown of a correlated system: The progressive collapse of the Mott-Hubbard state in
journal, August 2001
- Xu, W. M.; Naaman, O.; Rozenberg, G. Kh.
- Physical Review B, Vol. 64, Issue 9
Pressure Tuning of Electronic Energy Levels
journal, December 1982
- Drickamer, H. G.
- International Reviews in Physical Chemistry, Vol. 2, Issue 3
Emergent superconductivity in an iron-based honeycomb lattice initiated by pressure-driven spin-crossover
journal, May 2018
- Wang, Yonggang; Ying, Jianjun; Zhou, Zhengyang
- Nature Communications, Vol. 9, Issue 1
First-Order Isostructural Mott Transition in Highly Compressed MnO
journal, March 2005
- Yoo, C. S.; Maddox, B.; Klepeis, J. -H. P.
- Physical Review Letters, Vol. 94, Issue 11
Nature of the phase transition in spin crossover compounds
journal, January 1990
- Köhler, C. P.; Jakobi, R.; Meissner, E.
- Journal of Physics and Chemistry of Solids, Vol. 51, Issue 3
Zur frage der bindungsverhältnise in komplexverbindungen des eisen(II) mit 1,10-phenanthrolin
journal, April 1963
- Madeja, K.; König, E.
- Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 4
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Pair-distribution function and its coupling-constant average for the spin-polarized electron gas
journal, November 1992
- Perdew, John P.; Wang, Yue
- Physical Review B, Vol. 46, Issue 20
Reinvestigation of the iron-57 Moessbauer effect at high pressures in some iron(II) bis(phenanthroline) complexes
journal, December 1983
- Pebler, Juergen
- Inorganic Chemistry, Vol. 22, Issue 26
Spin Crossover in a Catenane Supramolecular System
journal, April 1995
- Real, J. A.; Andres, E.; Munoz, M. C.
- Science, Vol. 268, Issue 5208
Giant Resistance Change across the Phase Transition in Spin-Crossover Molecules
journal, May 2012
- Baadji, N.; Sanvito, S.
- Physical Review Letters, Vol. 108, Issue 21
Magnetic Collapse in Transition Metal Oxides at High Pressure: Implications for the Earth
journal, January 1997
- Cohen, R. E.
- Science, Vol. 275, Issue 5300
Complexes of Iron(II), Cobalt(II) and Nickel(II) with Biacetyl-bis-methylimine, 2-Pyridinal-methylimine and 2,6-Pyridindial-bis-methylimine
journal, February 1960
- Figgins, Paul E.; Busch, Daryle H.
- Journal of the American Chemical Society, Vol. 82, Issue 4
Negative-pressure-induced helimagnetism in ferromagnetic cubic perovskites
journal, October 2018
- Sakai, H.; Yokoyama, S.; Kuwabara, A.
- Physical Review Materials, Vol. 2, Issue 10
Ruby, metals, and as alternative pressure scales: A semiempirical description of shock-wave, ultrasonic, x-ray, and thermochemical data at high temperatures and pressures
journal, January 2007
- Dorogokupets, Peter I.; Oganov, Artem R.
- Physical Review B, Vol. 75, Issue 2
Electronic structure and magnetic properties of at high pressure
journal, May 1995
- Hearne, G. R.; Pasternak, M. P.; Taylor, R. D.
- Physical Review B, Vol. 51, Issue 17
Spin-Transition Polymers: From Molecular Materials Toward Memory Devices
journal, January 1998
- Kahn, O.
- Science, Vol. 279, Issue 5347
Synthesis and magnetic properties of double-perovskite oxide thin films
journal, February 2015
- Yoshimatsu, K.; Nogami, K.; Watarai, K.
- Physical Review B, Vol. 91, Issue 5
UNUSUAL MAGNETIC PROPERTIES OF SOME SIX-COÖRDINATE COBALT(II) COMPLEXES 1 —ELECTRONIC ISOMERS
journal, September 1961
- Stoufer, R. Carl; Busch, Daryle H.; Hadley, Wayne B.
- Journal of the American Chemical Society, Vol. 83, Issue 17
High-resolution manganese x-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity
journal, April 1994
- Peng, G.; deGroot, F. M. F.; Haemaelaeinen, K.
- Journal of the American Chemical Society, Vol. 116, Issue 7
Enforcing Multifunctionality: A Pressure-Induced Spin-Crossover Photomagnet
journal, July 2015
- Pinkowicz, Dawid; Rams, Michał; Mišek, Martin
- Journal of the American Chemical Society, Vol. 137, Issue 27
Works referencing / citing this record:
B-site disorder driven multiple-magnetic phases: Griffiths phase, re-entrant cluster glass, and exchange bias in Pr 2 CoFeO 6
journal, June 2019
- Pal, Arkadeb; Singh, Prajyoti; Gangwar, V. K.
- Applied Physics Letters, Vol. 114, Issue 25