High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)]

Hughey, Kendall D.; Lee, Minseong; Nam, Jisoo; Clune, Amanda J.; O’Neal, Kenneth R.; Tian, Wei; Fishman, Randy S.; Ozerov, Mykhaylo; Lee, JunHee; Zapf, Vivien S.; Musfeldt, Janice L.

doi:10.1021/acs.inorgchem.1c03311

Title: High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH₄)₂[FeCl₅·(H₂O)]

Abstract

We combine high field polarization, magneto-infrared spectroscopy, and lattice dynamics calculations with prior magnetization to explore the properties of (NH₄)₂[FeCl₅·(H₂O)]-a type II molecular multiferroic in which the mixing between charge, structure, and magnetism is controlled by intermolecular hydrogen and halogen bonds. Electric polarization is sensitive to the series of field-induced spin reorientations, increasing linearly with the field and reaching a maximum before collapsing to zero across the quasi-collinear to collinear-sinusoidal reorientation due to the restoration of inversion symmetry. Magnetoelectric coupling is on the order of 1.2 ps/m for the P∥c, H∥c configuration between 5 and 25 T at 1.5 K. In this range, the coupling takes place via an orbital hybridization mechanism. Other forms of mixing are active in (NH₄)₂[FeCl₅·(H₂O)] as well. Magneto-infrared spectroscopy reveals that all of the vibrational modes below 600 cm^–1 are sensitive to the field-induced transition to the fully saturated magnetic state at 30 T. We analyze these local lattice distortions and use frequency shifts to extract spin-phonon coupling constants for the Fe–O stretch, Fe–OH₂ rock, and NH₄⁺ libration. Inspection also reveals subtle symmetry breaking of the ammonium counterions across the ferroelectric transition. Here, the coexistence of such varied mixing processes in a platform with intermolecularmore »« less

Authors:

^[1]; Lee, Minseong ^[2]; Nam, Jisoo ^[3];

^[1];

^[4];

^[5];

^[3];

^[2];

^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Ulsan National Inst. of Science and Technology (Korea)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Florida State Univ., Tallahassee, FL (United States)

Publication Date:: Wed Feb 16 00:00:00 EST 2022

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1847496

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 61; Journal Issue: 8; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Magnetic properties; Quantum mechanics; Polarization; Phase transitions; Lattices

Citation Formats


                    Hughey, Kendall D., Lee, Minseong, Nam, Jisoo, Clune, Amanda J., O’Neal, Kenneth R., Tian, Wei, Fishman, Randy S., Ozerov, Mykhaylo, Lee, JunHee, Zapf, Vivien S., and Musfeldt, Janice L. High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)].  United States: N. p., 2022. 
Web.  doi:10.1021/acs.inorgchem.1c03311.

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                    Hughey, Kendall D., Lee, Minseong, Nam, Jisoo, Clune, Amanda J., O’Neal, Kenneth R., Tian, Wei, Fishman, Randy S., Ozerov, Mykhaylo, Lee, JunHee, Zapf, Vivien S., & Musfeldt, Janice L. High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)].  United States.  https://doi.org/10.1021/acs.inorgchem.1c03311

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                    Hughey, Kendall D., Lee, Minseong, Nam, Jisoo, Clune, Amanda J., O’Neal, Kenneth R., Tian, Wei, Fishman, Randy S., Ozerov, Mykhaylo, Lee, JunHee, Zapf, Vivien S., and Musfeldt, Janice L. Wed .  
"High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)]".  United States.  https://doi.org/10.1021/acs.inorgchem.1c03311.  https://www.osti.gov/servlets/purl/1847496.

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@article{osti_1847496,

  title        = {High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)]},

  author       = {Hughey, Kendall D. and Lee, Minseong and Nam, Jisoo and Clune, Amanda J. and O’Neal, Kenneth R. and Tian, Wei and Fishman, Randy S. and Ozerov, Mykhaylo and Lee, JunHee and Zapf, Vivien S. and Musfeldt, Janice L.},

  abstractNote = {We combine high field polarization, magneto-infrared spectroscopy, and lattice dynamics calculations with prior magnetization to explore the properties of (NH4)2[FeCl5·(H2O)]-a type II molecular multiferroic in which the mixing between charge, structure, and magnetism is controlled by intermolecular hydrogen and halogen bonds. Electric polarization is sensitive to the series of field-induced spin reorientations, increasing linearly with the field and reaching a maximum before collapsing to zero across the quasi-collinear to collinear-sinusoidal reorientation due to the restoration of inversion symmetry. Magnetoelectric coupling is on the order of 1.2 ps/m for the P∥c, H∥c configuration between 5 and 25 T at 1.5 K. In this range, the coupling takes place via an orbital hybridization mechanism. Other forms of mixing are active in (NH4)2[FeCl5·(H2O)] as well. Magneto-infrared spectroscopy reveals that all of the vibrational modes below 600 cm–1 are sensitive to the field-induced transition to the fully saturated magnetic state at 30 T. We analyze these local lattice distortions and use frequency shifts to extract spin-phonon coupling constants for the Fe–O stretch, Fe–OH2 rock, and NH4+ libration. Inspection also reveals subtle symmetry breaking of the ammonium counterions across the ferroelectric transition. Here, the coexistence of such varied mixing processes in a platform with intermolecular hydrogen- and halogen-bonding opens the door to greater understanding of multiferroics and magnetoelectrics governed by through-space interactions.},

  doi          = {10.1021/acs.inorgchem.1c03311},

  journal      = {Inorganic Chemistry},

  number       = 8,

  volume       = 61,

  place        = {United States},

  year         = {Wed Feb 16 00:00:00 EST 2022},

  month        = {Wed Feb 16 00:00:00 EST 2022}

}

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Works referenced in this record:

A new pathway of preparation and refined structure of (NH4)2[FeCl5(H2O)]
journal, April 2013

Lacková, Darina; Ondrejkovičová, Iveta; Koman, Marián
Acta Chimica Slovaca, Vol. 6, Issue 1
DOI: 10.2478/acs-2013-0020

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
DOI: 10.1103/PhysRevLett.77.3865

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets
journal, May 2014

Lancaster, T.; Goddard, P. A.; Blundell, S. J.
Physical Review Letters, Vol. 112, Issue 20
DOI: 10.1103/PhysRevLett.112.207201

The Halogen Bond
journal, January 2016

Cavallo, Gabriella; Metrangolo, Pierangelo; Milani, Roberto
Chemical Reviews, Vol. 116, Issue 4
DOI: 10.1021/acs.chemrev.5b00484

Infrared Studies of Water in Crystalline Hydrates: K ₂ FeCl ₅ ·H ₂ O (Erythrosiderite) and Related Aquopentachloroferrates(III)
journal, January 1975

Falk, Michael; Huang, Chung-Hsi; Knop, Osvald
Canadian Journal of Chemistry, Vol. 53, Issue 1
DOI: 10.1139/v75-006

Large spin-phonon coupling and magnetically induced phonon anisotropy in Sr $M$ O $_{3}$ perovskites ( $M = V$ ,Cr,Mn,Fe,Co)
journal, September 2011

Lee, Jun Hee; Rabe, Karin M.
Physical Review B, Vol. 84, Issue 10
DOI: 10.1103/PhysRevB.84.104440

Projector augmented-wave method
journal, December 1994

Blöchl, P. E.
Physical Review B, Vol. 50, Issue 24, p. 17953-17979
DOI: 10.1103/PhysRevB.50.17953

A survey study of the vibrational spectra of some aquo-halogenocomplexes
journal, January 1971

Adams, D. M.; Lock, P. J.
Journal of the Chemical Society A: Inorganic, Physical, Theoretical
DOI: 10.1039/j19710002801

Magnetic field-temperature phase diagram of multiferroic $[{({CH}_{3})}_{2} {NH}_{2}] Mn {(HCOO)}_{3}$
journal, September 2017

Clune, A. J.; Hughey, K. D.; Lee, C.
Physical Review B, Vol. 96, Issue 10
DOI: 10.1103/PhysRevB.96.104424

Electronic phase separation and magnetic-field-induced phenomena in molecular multiferroic $({ND}_{4})_{2} {FeCl}_{5} \cdot D_{2} O$
journal, August 2018

Tian, W.; Cao, H. B.; Clune, Amanda J.
Physical Review B, Vol. 98, Issue 5
DOI: 10.1103/PhysRevB.98.054407

Crystal structure of diammonium aquapentachloroferrate(III)
journal, January 1978

Figgis, Bn; Raston, Cl; Sharma, Rp
Australian Journal of Chemistry, Vol. 31, Issue 12
DOI: 10.1071/CH9782717

Multiferroics of spin origin
journal, July 2014

Tokura, Yoshinori; Seki, Shinichiro; Nagaosa, Naoto
Reports on Progress in Physics, Vol. 77, Issue 7
DOI: 10.1088/0034-4885/77/7/076501

Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O
journal, August 2019

Clune, Amanda J.; Nam, Jisoo; Lee, Minseong
npj Quantum Materials, Vol. 4, Issue 1
DOI: 10.1038/s41535-019-0180-1

Microscopic mechanisms of spin-dependent electric polarization in $3 d$ oxides
journal, July 2008

Moskvin, A. S.; Drechsler, S. -L.
Physical Review B, Vol. 78, Issue 2
DOI: 10.1103/PhysRevB.78.024102

Above-Room-Temperature Magnetodielectric Coupling in a Possible Molecule-Based Multiferroic: Triethylmethylammonium Tetrabromoferrate(III)
journal, November 2012

Cai, Hong-Ling; Zhang, Yi; Fu, Da-Wei
Journal of the American Chemical Society, Vol. 134, Issue 45
DOI: 10.1021/ja3073319

Commensurate magnetic structures of $R {Mn}_{2} O_{5}$ $(R = Y, Ho, Bi)$ determined by single-crystal neutron diffraction
journal, April 2008

Vecchini, C.; Chapon, L. C.; Brown, P. J.
Physical Review B, Vol. 77, Issue 13
DOI: 10.1103/PhysRevB.77.134434

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Thermodynamic properties of the new multiferroic material (NH ₄ ) ₂ [FeCl ₅ (H ₂ O)]
journal, December 2013

Ackermann, M.; Brüning, D.; Lorenz, T.
New Journal of Physics, Vol. 15, Issue 12
DOI: 10.1088/1367-2630/15/12/123001

Exchange interaction mediated ferroelectricity in multiferroic MnTiO ₃ with anisotropic orbital hybridization and hole delocalization
journal, February 2014

Chen, S. W.; Lin, P. A.; Jeng, H. T.
Applied Physics Letters, Vol. 104, Issue 8
DOI: 10.1063/1.4866462

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
Physical Review B, Vol. 57, Issue 3, p. 1505-1509
DOI: 10.1103/PhysRevB.57.1505

Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an $S = 1$ quantum antiferromagnet
journal, April 2017

Brambleby, Jamie; Manson, Jamie L.; Goddard, Paul A.
Physical Review B, Vol. 95, Issue 13
DOI: 10.1103/PhysRevB.95.134435

The Role of Order–Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron(II)–Iron(III) Formate Framework
journal, November 2012

Cañadillas-Delgado, Laura; Fabelo, Oscar; Rodríguez-Velamazán, J. Alberto
Journal of the American Chemical Society, Vol. 134, Issue 48
DOI: 10.1021/ja3082457

Magnetic phase transitions and magnetoelastic coupling in $S = \frac{1}{2}$ Heisenberg antiferromagnets
journal, March 2017

al-Wahish, Amal; O'Neal, K. R.; Lee, C.
Physical Review B, Vol. 95, Issue 10
DOI: 10.1103/PhysRevB.95.104437

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism
journal, August 2012

Lunkenheimer, Peter; Müller, Jens; Krohns, Stephan
Nature Materials, Vol. 11, Issue 9
DOI: 10.1038/nmat3400

Magnetic excitations of the hybrid multiferroic $({ND}_{4})_{2} {FeCl}_{5} \cdot D_{2} O$
journal, June 2021

Bai, Xiaojian; Fishman, Randy S.; Sala, Gabriele
Physical Review B, Vol. 103, Issue 22
DOI: 10.1103/PhysRevB.103.224411

Magnetically-induced ferroelectricity in the (ND4)2[FeCl5(D2O)] molecular compound
journal, September 2015

Alberto Rodríguez-Velamazán, José; Fabelo, Óscar; Millán, Ángel
Scientific Reports, Vol. 5, Issue 1
DOI: 10.1038/srep14475

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Kresse, G.; Hafner, J.
Physical Review B, Vol. 47, Issue 1, p. 558-561
DOI: 10.1103/PhysRevB.47.558

Electric polarization observed in single crystals of multiferroic ${Lu}_{2} {MnCoO}_{6}$
journal, May 2016

Chikara, S.; Singleton, J.; Bowlan, J.
Physical Review B, Vol. 93, Issue 18
DOI: 10.1103/PhysRevB.93.180405

Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal-Organic Framework
journal, February 2013

Stroppa, A.; Barone, P.; Jain, P.
Advanced Materials, Vol. 25, Issue 16
DOI: 10.1002/adma.201204738

Magnetoelectric effects in an organometallic quantum magnet
journal, April 2011

Zapf, V. S.; Sengupta, P.; Batista, C. D.
Physical Review B, Vol. 83, Issue 14
DOI: 10.1103/PhysRevB.83.140405

Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX ₃ Architecture
journal, September 2009

Jain, Prashant; Ramachandran, Vasanth; Clark, Ronald J.
Journal of the American Chemical Society, Vol. 131, Issue 38
DOI: 10.1021/ja904156s

Laser-Raman spectra of crystalline (NH4)2FeCl5.H2O, K2FeCl5.H2O and K2FeCl5.D2O
journal, May 1974

Sharma, Shiv Kumar; Pandya, D. K.
Journal of Inorganic and Nuclear Chemistry, Vol. 36, Issue 5
DOI: 10.1016/0022-1902(74)80235-6

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy
journal, June 2010

Karhánek, David; Bučko, Tomáš; Hafner, Jürgen
Journal of Physics: Condensed Matter, Vol. 22, Issue 26
DOI: 10.1088/0953-8984/22/26/265006

The dimensionality of ammonium reorientation in (NH ₄ ) ₂ S ₂ O ₈ : the view from neutron spectroscopy
journal, March 2008

Prager, M.; Grimm, H.; Natkaniec, I.
Journal of Physics: Condensed Matter, Vol. 20, Issue 12
DOI: 10.1088/0953-8984/20/12/125218

Single-crystal pulsed neutron diffraction structure of the antiferromagnet K ₂ [FeCl ₅ (H ₂ O)] with and without applied pressure
journal, February 1995

Schultz, A. J.; Carlin, R. L.
Acta Crystallographica Section B Structural Science, Vol. 51, Issue 1
DOI: 10.1107/S0108768194008438

Metamagnetic transitions and magnetoelectricity in the spin-1 honeycomb antiferromagnet ${Ni}_{2} {Mo}_{3} O_{8}$
journal, January 2021

Tang, Y. S.; Zhang, J. H.; Lin, L.
Physical Review B, Vol. 103, Issue 1
DOI: 10.1103/PhysRevB.103.014112

Vibrational Spectra of NH4Sm(SO4)2·4H2O and NH4Ln(SO4)2·2H2O[Ln= Yb, Tm]
journal, February 1996

Suresh, G.; Ratheesh, R.; Pradip, T.
Journal of Solid State Chemistry, Vol. 121, Issue 2
DOI: 10.1006/jssc.1996.0055

Raman spectra of NH ₄ Cl and NH ₄ Br: Dependence of the librational and the internal modes of the NH4+ ion on volume and on nitrogen‐halogen distance
journal, October 1974

Ebisuzaki, Y.
The Journal of Chemical Physics, Vol. 61, Issue 8
DOI: 10.1063/1.1682473

Magnetic-field-induced change of magnetoelectric coupling in the hybrid multiferroic ${(N D_{4})}_{2} [FeC l_{5} \cdot D_{2} O]$
journal, May 2017

Rodríguez-Velamazán, J. Alberto; Fabelo, Oscar; Campo, Javier
Physical Review B, Vol. 95, Issue 17
DOI: 10.1103/PhysRevB.95.174439

Low-temperature tunneling and rotational dynamics of the ammonium cations in (NH ₄ ) ₂ B ₁₂ H ₁₂
journal, September 2011

Verdal, Nina; Udovic, Terrence J.; Rush, John J.
The Journal of Chemical Physics, Vol. 135, Issue 9
DOI: 10.1063/1.3624495

Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers
journal, February 2020

Hughey, Kendall D.; Harms, Nathan C.; O’Neal, Kenneth R.
Inorganic Chemistry, Vol. 59, Issue 4
DOI: 10.1021/acs.inorgchem.9b02394

Phase transitions of the ferroelectric ${({ND}_{4})}_{2} {FeCl}_{5} \cdot D_{2} O$ under magnetic field
journal, August 2021

Li, Shaozhi; Fishman, Randy S.
Physical Review B, Vol. 104, Issue 6
DOI: 10.1103/PhysRevB.104.L060407

Spin-lattice interactions through the quantum critical transition in $Cu (pyz) {({NO}_{3})}_{2}$
journal, March 2010

Günaydın-Şen, Ö.; Lee, C.; Tung, L. C.
Physical Review B, Vol. 81, Issue 10
DOI: 10.1103/PhysRevB.81.104307

Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001

Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea
Reviews of Modern Physics, Vol. 73, Issue 2
DOI: 10.1103/RevModPhys.73.515

Microscopic Theory of Force Constants in the Adiabatic Approximation
journal, January 1970

Pick, Robert M.; Cohen, Morrel H.; Martin, Richard M.
Physical Review B, Vol. 1, Issue 2
DOI: 10.1103/PhysRevB.1.910

Magnetic Ordering-Induced Multiferroic Behavior in [CH ₃ NH ₃ ][Co(HCOO) ₃ ] Metal–Organic Framework
journal, January 2016

Gómez-Aguirre, L. Claudia; Pato-Doldán, Breogán; Mira, J.
Journal of the American Chemical Society, Vol. 138, Issue 4
DOI: 10.1021/jacs.5b11688

Magnetic ordering effects in the Raman spectra of ${La}_{1 - x} {Mn}_{1 - x} O_{3}$
journal, November 1999

Granado, E.; García, A.; Sanjurjo, J. A.
Physical Review B, Vol. 60, Issue 17
DOI: 10.1103/PhysRevB.60.11879

Magnetically induced electric polarization in an organometallic magnet
journal, August 2010

Zapf, V. S.; Kenzelmann, M.; Wolff-Fabris, F.
Physical Review B, Vol. 82, Issue 6
DOI: 10.1103/PhysRevB.82.060402

Understanding magnetic interactions in the series $A_{2} Fe X_{5} \cdot H_{2} O$ ( $A = K$ , Rb; $X = Cl$ , Br). II. Inelastic neutron scattering and DFT studies
journal, August 2008

Campo, Javier; Luzón, Javier; Palacio, Fernando
Physical Review B, Vol. 78, Issue 5
DOI: 10.1103/PhysRevB.78.054415

Special points for Brillouin-zone integrations
journal, June 1976

Monkhorst, Hendrik J.; Pack, James D.
Physical Review B, Vol. 13, Issue 12, p. 5188-5192
DOI: 10.1103/PhysRevB.13.5188

Structure–Property Relations in Multiferroic [(CH ₃ ) ₂ NH ₂ ] M (HCOO) ₃ ( M = Mn, Co, Ni)
journal, August 2018

Hughey, Kendall D.; Clune, Amanda J.; Yokosuk, Michael O.
Inorganic Chemistry, Vol. 57, Issue 18
DOI: 10.1021/acs.inorgchem.8b01609

Ferroelectricity Induced by Spin-Dependent Metal-Ligand Hybridization in ${Ba}_{2} {CoGe}_{2} O_{7}$
journal, September 2010

Murakawa, H.; Onose, Y.; Miyahara, S.
Physical Review Letters, Vol. 105, Issue 13
DOI: 10.1103/PhysRevLett.105.137202

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
DOI: 10.1103/PhysRevB.54.11169

Linear optical properties in the projector-augmented wave methodology
journal, January 2006

Gajdoš, M.; Hummer, K.; Kresse, G.
Physical Review B, Vol. 73, Issue 4
DOI: 10.1103/PhysRevB.73.045112

Interfacial Structure of Manganite Superlattice
journal, July 2011

Yamasaki, Yoshihiro; Okuyama, Daisuke; Nakamura, Masao
Journal of the Physical Society of Japan, Vol. 80, Issue 7
DOI: 10.1143/JPSJ.80.073601

Classifying multiferroics: Mechanisms and effects
journal, March 2009

Khomskii, Daniel
Physics, Vol. 2
DOI: 10.1103/Physics.2.20

Spin-lattice coupling mediated multiferroicity in ${({ND}_{4})}_{2} {FeCl}_{5} \cdot D_{2} O$
journal, December 2016

Tian, W.; Cao, Huibo; Wang, Jincheng
Physical Review B, Vol. 94, Issue 21
DOI: 10.1103/PhysRevB.94.214405

Perturbation expansion of variational principles at arbitrary order
journal, August 1995

Gonze, Xavier
Physical Review A, Vol. 52, Issue 2
DOI: 10.1103/PhysRevA.52.1086

Dynamical matrices, Born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory
journal, April 1997

Gonze, Xavier; Lee, Changyol
Physical Review B, Vol. 55, Issue 16
DOI: 10.1103/PhysRevB.55.10355

Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets
journal, July 2012

Pardo, Emilio; Train, Cyrille; Liu, Hongbo
Angewandte Chemie International Edition, Vol. 51, Issue 33
DOI: 10.1002/anie.201202848

Multiferroics: a magnetic twist for ferroelectricity
journal, January 2007

Cheong, Sang-Wook; Mostovoy, Maxim
Nature Materials, Vol. 6, Issue 1
DOI: 10.1038/nmat1804

Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers
journal, July 2012

Bosch-Serrano, Cristian; Clemente-Juan, Juan M.; Coronado, Eugenio
Physical Review B, Vol. 86, Issue 2
DOI: 10.1103/PhysRevB.86.024432

Nonisomorphic antiferromagnetic behavior of two isomorphic salts: low-temperature heat capacities and magnetic susceptibilities of diammonium iron pentachloride monohydrate and dipotassium iron pentachloride monohydrate
journal, May 1978

McElearney, J. N.; Merchant, S.
Inorganic Chemistry, Vol. 17, Issue 5
DOI: 10.1021/ic50183a024

Microscopic theory of spin-polarization coupling in multiferroic transition metal oxides
journal, October 2007

Jia, Chenglong; Onoda, Shigeki; Nagaosa, Naoto
Physical Review B, Vol. 76, Issue 14
DOI: 10.1103/PhysRevB.76.144424

Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory
journal, July 2005

Wu, Xifan; Vanderbilt, David; Hamann, D. R.
Physical Review B, Vol. 72, Issue 3
DOI: 10.1103/PhysRevB.72.035105

Switchable electric polarization and ferroelectric domains in a metal-organic-framework
journal, September 2016

Jain, Prashant; Stroppa, Alessandro; Nabok, Dmitrii
npj Quantum Materials, Vol. 1, Issue 1
DOI: 10.1038/npjquantmats.2016.12

Magnetoelectric coupling in the mixed erythrosiderite ${[{({NH}_{4})}_{1 - x} K_{x}]}_{2} [Fe {Cl}_{5} (H_{2} O)]$
journal, August 2020

Brüning, Daniel; Fröhlich, Tobias; Langenbach, Malte
Physical Review B, Vol. 102, Issue 5
DOI: 10.1103/PhysRevB.102.054413

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Most research on multiferroics and magnetoelectric effects to date has focused on inorganic oxides. Molecule-based materials are a relatively new field in which to search for magnetoelectric multiferroics and to explore new coupling mechanisms between electric and magnetic order. We present magnetoelectric behavior in NiCl ₂ -4SC(NH ₂ ) ₂ (DTN) and CoCl ₂ -4SC(NH ₂ ) ₂ (DTC). These compounds form tetragonal structures where the transition metal ion (Ni or Co) is surrounded by four electrically polar thiourea molecules [SC(NH ₂ ) ₂ ]. By tracking the magnetic and electric properties of these compounds as a function of magneticmore »« less
Cited by 8
https://doi.org/10.1155/2014/512621
Spin-lattice coupling mediated multiferroicity in (ND₄)₂FeCl₅ • D₂O

Journal Article Tian, Wei ; Cao, Huibo ; Wang, Jincheng ; ... - Physical Review B

In this paper, we report a neutron diffraction study of the multiferroic mechanism in (ND₄)₂FeCl₅ • D₂O, a molecular compound that exhibits magnetically induced ferroelectricity. This material exhibits two successive magnetic transitions on cooling: a long-range order transition to an incommensurate (IC) collinear sinusoidal spin state at T_N = 7.3 K, followed by a second transition to an IC cycloidal spin state at T_FE = 6.8 K, the latter of which is accompanied by spontaneous ferroelectric polarization. The cycloid structure is strongly distorted by spin-lattice coupling, as evidenced by the observations of both odd and even higher-order harmonics associated withmore »« less
Cited by 15
https://doi.org/10.1103/PhysRevB.94.214405

Full Text Available
Magnetic excitations of the hybrid multiferroic (ND₄)₂FeCl₅·D₂O

Journal Article Bai, Xiaojian ; Tian, Wei ; Fishman, Randy ; ... - Physical Review B

We repormore »« less
https://doi.org/10.1103/physrevb.103.224411

Full Text Available

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Title: High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH4)2[FeCl5·(H2O)]

Abstract

Citation Formats

A new pathway of preparation and refined structure of (NH4)2[FeCl5(H2O)] journal, April 2013

Generalized Gradient Approximation Made Simple journal, October 1996

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets journal, May 2014

The Halogen Bond journal, January 2016

Infrared Studies of Water in Crystalline Hydrates: K 2 FeCl 5 ·H 2 O (Erythrosiderite) and Related Aquopentachloroferrates(III) journal, January 1975

Large spin-phonon coupling and magnetically induced phonon anisotropy in Sr M O 3 perovskites ( M = V ,Cr,Mn,Fe,Co) journal, September 2011

Projector augmented-wave method journal, December 1994

A survey study of the vibrational spectra of some aquo-halogenocomplexes journal, January 1971

Magnetic field-temperature phase diagram of multiferroic [ ( CH 3 ) 2 NH 2 ] Mn ( HCOO ) 3 journal, September 2017

Electronic phase separation and magnetic-field-induced phenomena in molecular multiferroic ( ND 4 ) 2 FeCl 5 · D 2 O journal, August 2018

Crystal structure of diammonium aquapentachloroferrate(III) journal, January 1978

Multiferroics of spin origin journal, July 2014

Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O journal, August 2019

Microscopic mechanisms of spin-dependent electric polarization in 3 d oxides journal, July 2008

Above-Room-Temperature Magnetodielectric Coupling in a Possible Molecule-Based Multiferroic: Triethylmethylammonium Tetrabromoferrate(III) journal, November 2012

Commensurate magnetic structures of R Mn 2 O 5 ( R = Y , Ho , Bi ) determined by single-crystal neutron diffraction journal, April 2008

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Thermodynamic properties of the new multiferroic material (NH 4 ) 2 [FeCl 5 (H 2 O)] journal, December 2013

Exchange interaction mediated ferroelectricity in multiferroic MnTiO 3 with anisotropic orbital hybridization and hole delocalization journal, February 2014

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S = 1 quantum antiferromagnet journal, April 2017

The Role of Order–Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron(II)–Iron(III) Formate Framework journal, November 2012

Magnetic phase transitions and magnetoelastic coupling in S = 1 2 Heisenberg antiferromagnets journal, March 2017

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism journal, August 2012

Magnetic excitations of the hybrid multiferroic ( ND 4 ) 2 FeCl 5 · D 2 O journal, June 2021

Magnetically-induced ferroelectricity in the (ND4)2[FeCl5(D2O)] molecular compound journal, September 2015

Ab initiomolecular dynamics for liquid metals journal, January 1993

Electric polarization observed in single crystals of multiferroic Lu 2 MnCoO 6 journal, May 2016

Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal-Organic Framework journal, February 2013

Magnetoelectric effects in an organometallic quantum magnet journal, April 2011

Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX 3 Architecture journal, September 2009

Laser-Raman spectra of crystalline (NH4)2FeCl5.H2O, K2FeCl5.H2O and K2FeCl5.D2O journal, May 1974

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy journal, June 2010

The dimensionality of ammonium reorientation in (NH 4 ) 2 S 2 O 8 : the view from neutron spectroscopy journal, March 2008

Single-crystal pulsed neutron diffraction structure of the antiferromagnet K 2 [FeCl 5 (H 2 O)] with and without applied pressure journal, February 1995

Metamagnetic transitions and magnetoelectricity in the spin-1 honeycomb antiferromagnet Ni 2 Mo 3 O 8 journal, January 2021

Vibrational Spectra of NH4Sm(SO4)2·4H2O and NH4Ln(SO4)2·2H2O[Ln= Yb, Tm] journal, February 1996

Raman spectra of NH 4 Cl and NH 4 Br: Dependence of the librational and the internal modes of the NH4+ ion on volume and on nitrogen‐halogen distance journal, October 1974

Magnetic-field-induced change of magnetoelectric coupling in the hybrid multiferroic ( N D 4 ) 2 [ FeC l 5 · D 2 O ] journal, May 2017

Low-temperature tunneling and rotational dynamics of the ammonium cations in (NH 4 ) 2 B 12 H 12 journal, September 2011

Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers journal, February 2020

Phase transitions of the ferroelectric ( ND 4 ) 2 FeCl 5 · D 2 O under magnetic field journal, August 2021

Spin-lattice interactions through the quantum critical transition in Cu ( pyz ) ( NO 3 ) 2 journal, March 2010

Phonons and related crystal properties from density-functional perturbation theory journal, July 2001

Microscopic Theory of Force Constants in the Adiabatic Approximation journal, January 1970

Magnetic Ordering-Induced Multiferroic Behavior in [CH 3 NH 3 ][Co(HCOO) 3 ] Metal–Organic Framework journal, January 2016

Magnetic ordering effects in the Raman spectra of La 1 − x Mn 1 − x O 3 journal, November 1999

Magnetically induced electric polarization in an organometallic magnet journal, August 2010

Understanding magnetic interactions in the series A 2 Fe X 5 ⋅ H 2 O ( A = K , Rb; X = Cl , Br). II. Inelastic neutron scattering and DFT studies journal, August 2008

Special points for Brillouin-zone integrations journal, June 1976

Structure–Property Relations in Multiferroic [(CH 3 ) 2 NH 2 ] M (HCOO) 3 ( M = Mn, Co, Ni) journal, August 2018

Ferroelectricity Induced by Spin-Dependent Metal-Ligand Hybridization in Ba 2 CoGe 2 O 7 journal, September 2010

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Linear optical properties in the projector-augmented wave methodology journal, January 2006

Interfacial Structure of Manganite Superlattice journal, July 2011

Classifying multiferroics: Mechanisms and effects journal, March 2009

Spin-lattice coupling mediated multiferroicity in ( ND 4 ) 2 FeCl 5 · D 2 O journal, December 2016

Perturbation expansion of variational principles at arbitrary order journal, August 1995

Dynamical matrices, Born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory journal, April 1997

Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets journal, July 2012

Multiferroics: a magnetic twist for ferroelectricity journal, January 2007

Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers journal, July 2012

Nonisomorphic antiferromagnetic behavior of two isomorphic salts: low-temperature heat capacities and magnetic susceptibilities of diammonium iron pentachloride monohydrate and dipotassium iron pentachloride monohydrate journal, May 1978

Microscopic theory of spin-polarization coupling in multiferroic transition metal oxides journal, October 2007

Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory journal, July 2005

Switchable electric polarization and ferroelectric domains in a metal-organic-framework journal, September 2016

Magnetoelectric coupling in the mixed erythrosiderite [ ( NH 4 ) 1 − x K x ] 2 [ Fe Cl 5 ( H 2 O ) ] journal, August 2020

Title: High-Field Magnetoelectric and Spin-Phonon Coupling in Multiferroic (NH₄)₂[FeCl₅·(H₂O)]

A new pathway of preparation and refined structure of (NH4)2[FeCl5(H2O)]
journal, April 2013

Generalized Gradient Approximation Made Simple
journal, October 1996

Controlling Magnetic Order and Quantum Disorder in Molecule-Based Magnets
journal, May 2014

The Halogen Bond
journal, January 2016

Infrared Studies of Water in Crystalline Hydrates: K ₂ FeCl ₅ ·H ₂ O (Erythrosiderite) and Related Aquopentachloroferrates(III)
journal, January 1975

Large spin-phonon coupling and magnetically induced phonon anisotropy in Sr $M$ O $_{3}$ perovskites ( $M = V$ ,Cr,Mn,Fe,Co)
journal, September 2011

Projector augmented-wave method
journal, December 1994

A survey study of the vibrational spectra of some aquo-halogenocomplexes
journal, January 1971

Magnetic field-temperature phase diagram of multiferroic $[{({CH}_{3})}_{2} {NH}_{2}] Mn {(HCOO)}_{3}$
journal, September 2017

Electronic phase separation and magnetic-field-induced phenomena in molecular multiferroic $({ND}_{4})_{2} {FeCl}_{5} \cdot D_{2} O$
journal, August 2018

Crystal structure of diammonium aquapentachloroferrate(III)
journal, January 1978

Multiferroics of spin origin
journal, July 2014

Magnetic field-temperature phase diagram of multiferroic (NH4)2FeCl5·H2O
journal, August 2019

Microscopic mechanisms of spin-dependent electric polarization in $3 d$ oxides
journal, July 2008

Above-Room-Temperature Magnetodielectric Coupling in a Possible Molecule-Based Multiferroic: Triethylmethylammonium Tetrabromoferrate(III)
journal, November 2012

Commensurate magnetic structures of $R {Mn}_{2} O_{5}$ $(R = Y, Ho, Bi)$ determined by single-crystal neutron diffraction
journal, April 2008

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Thermodynamic properties of the new multiferroic material (NH ₄ ) ₂ [FeCl ₅ (H ₂ O)]
journal, December 2013

Exchange interaction mediated ferroelectricity in multiferroic MnTiO ₃ with anisotropic orbital hybridization and hole delocalization
journal, February 2014

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an $S = 1$ quantum antiferromagnet
journal, April 2017

The Role of Order–Disorder Transitions in the Quest for Molecular Multiferroics: Structural and Magnetic Neutron Studies of a Mixed Valence Iron(II)–Iron(III) Formate Framework
journal, November 2012

Magnetic phase transitions and magnetoelastic coupling in $S = \frac{1}{2}$ Heisenberg antiferromagnets
journal, March 2017

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism
journal, August 2012

Magnetic excitations of the hybrid multiferroic $({ND}_{4})_{2} {FeCl}_{5} \cdot D_{2} O$
journal, June 2021

Magnetically-induced ferroelectricity in the (ND4)2[FeCl5(D2O)] molecular compound
journal, September 2015

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Electric polarization observed in single crystals of multiferroic ${Lu}_{2} {MnCoO}_{6}$
journal, May 2016

Hybrid Improper Ferroelectricity in a Multiferroic and Magnetoelectric Metal-Organic Framework
journal, February 2013

Magnetoelectric effects in an organometallic quantum magnet
journal, April 2011

Multiferroic Behavior Associated with an Order−Disorder Hydrogen Bonding Transition in Metal−Organic Frameworks (MOFs) with the Perovskite ABX ₃ Architecture
journal, September 2009

Laser-Raman spectra of crystalline (NH4)2FeCl5.H2O, K2FeCl5.H2O and K2FeCl5.D2O
journal, May 1974

A density-functional study of the adsorption of methane-thiol on the (111) surfaces of the Ni-group metals: II. Vibrational spectroscopy
journal, June 2010

The dimensionality of ammonium reorientation in (NH ₄ ) ₂ S ₂ O ₈ : the view from neutron spectroscopy
journal, March 2008

Single-crystal pulsed neutron diffraction structure of the antiferromagnet K ₂ [FeCl ₅ (H ₂ O)] with and without applied pressure
journal, February 1995

Metamagnetic transitions and magnetoelectricity in the spin-1 honeycomb antiferromagnet ${Ni}_{2} {Mo}_{3} O_{8}$
journal, January 2021

Vibrational Spectra of NH4Sm(SO4)2·4H2O and NH4Ln(SO4)2·2H2O[Ln= Yb, Tm]
journal, February 1996

Raman spectra of NH ₄ Cl and NH ₄ Br: Dependence of the librational and the internal modes of the NH4+ ion on volume and on nitrogen‐halogen distance
journal, October 1974

Magnetic-field-induced change of magnetoelectric coupling in the hybrid multiferroic ${(N D_{4})}_{2} [FeC l_{5} \cdot D_{2} O]$
journal, May 2017

Low-temperature tunneling and rotational dynamics of the ammonium cations in (NH ₄ ) ₂ B ₁₂ H ₁₂
journal, September 2011

Spin–Lattice Coupling Across the Magnetic Quantum-Phase Transition in Copper-Containing Coordination Polymers
journal, February 2020

Phase transitions of the ferroelectric ${({ND}_{4})}_{2} {FeCl}_{5} \cdot D_{2} O$ under magnetic field
journal, August 2021

Spin-lattice interactions through the quantum critical transition in $Cu (pyz) {({NO}_{3})}_{2}$
journal, March 2010

Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001

Microscopic Theory of Force Constants in the Adiabatic Approximation
journal, January 1970

Magnetic Ordering-Induced Multiferroic Behavior in [CH ₃ NH ₃ ][Co(HCOO) ₃ ] Metal–Organic Framework
journal, January 2016

Magnetic ordering effects in the Raman spectra of ${La}_{1 - x} {Mn}_{1 - x} O_{3}$
journal, November 1999

Magnetically induced electric polarization in an organometallic magnet
journal, August 2010

Understanding magnetic interactions in the series $A_{2} Fe X_{5} \cdot H_{2} O$ ( $A = K$ , Rb; $X = Cl$ , Br). II. Inelastic neutron scattering and DFT studies
journal, August 2008

Special points for Brillouin-zone integrations
journal, June 1976

Structure–Property Relations in Multiferroic [(CH ₃ ) ₂ NH ₂ ] M (HCOO) ₃ ( M = Mn, Co, Ni)
journal, August 2018

Ferroelectricity Induced by Spin-Dependent Metal-Ligand Hybridization in ${Ba}_{2} {CoGe}_{2} O_{7}$
journal, September 2010

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Linear optical properties in the projector-augmented wave methodology
journal, January 2006

Interfacial Structure of Manganite Superlattice
journal, July 2011

Classifying multiferroics: Mechanisms and effects
journal, March 2009

Spin-lattice coupling mediated multiferroicity in ${({ND}_{4})}_{2} {FeCl}_{5} \cdot D_{2} O$
journal, December 2016

Perturbation expansion of variational principles at arbitrary order
journal, August 1995

Dynamical matrices, Born effective charges, dielectric permittivity tensors, and interatomic force constants from density-functional perturbation theory
journal, April 1997

Multiferroics by Rational Design: Implementing Ferroelectricity in Molecule-Based Magnets
journal, July 2012

Multiferroics: a magnetic twist for ferroelectricity
journal, January 2007

Molecular analog of multiferroics: Electric and magnetic field effects in many-electron mixed-valence dimers
journal, July 2012

Nonisomorphic antiferromagnetic behavior of two isomorphic salts: low-temperature heat capacities and magnetic susceptibilities of diammonium iron pentachloride monohydrate and dipotassium iron pentachloride monohydrate
journal, May 1978

Microscopic theory of spin-polarization coupling in multiferroic transition metal oxides
journal, October 2007

Systematic treatment of displacements, strains, and electric fields in density-functional perturbation theory
journal, July 2005

Switchable electric polarization and ferroelectric domains in a metal-organic-framework
journal, September 2016

Magnetoelectric coupling in the mixed erythrosiderite ${[{({NH}_{4})}_{1 - x} K_{x}]}_{2} [Fe {Cl}_{5} (H_{2} O)]$
journal, August 2020