Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a quantum antiferromagnet]
Abstract
The magnetic ground state of the quasi-one-dimensional spin-1 antiferromagnetic chain is sensitive to the relative sizes of the single-ion anisotropy (D) and the intrachain (J) and interchain (J') exchange interactions. The ratios D/J and J' /J dictate the material's placement in one of three competing phases: a Haldane gapped phase, a quantum paramagnet, and an XY-ordered state, with a quantum critical point at their junction. We have identified [Ni(HF2)(pyz)2] SbF6, where pyz = pyrazine, as a rare candidate in which this behavior can be explored in detail. Combining neutron scattering (elastic and inelastic) in applied magnetic fields of up to 10 tesla and magnetization measurements in fields of up to 60 tesla with numerical modeling of experimental observables, we are able to obtain accurate values of all of the parameters of the Hamiltonian [D = 13.3(1) K, J = 10.4(3) K, and J' = 1.4(2) K], despite the polycrystalline nature of the sample. Density-functional theory calculations result in similar couplings (J = 9.2 K, J' = 1.8 K) and predict that the majority of the total spin population resides on the Ni(II) ion, while the remaining spin density is delocalized over both ligand types. Finally, the general procedures outlined inmore »
- Authors:
-
- Univ. of Warwick, Coventry (United Kingdom)
- Eastern Washington Univ., Cheney, WA (United States); National Institute of Standards and Technology, Gaithersburg, MD (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Oxford, Oxford (United Kingdom); STFC Rutherford Appleton Lab., Oxfordshire (United Kingdom)
- STFC Rutherford Appleton Lab., Oxfordshire (United Kingdom)
- Eastern Washington Univ., Cheney, WA (United States)
- National Institute of Standards and Technology, Gaithersburg, MD (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Bern, Bern (Switzerland)
- Univ. of Oxford, Oxford (United Kingdom); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1373946
- Alternate Identifier(s):
- OSTI ID: 1352461; OSTI ID: 1407877; OSTI ID: 1471948
- Report Number(s):
- LA-UR-16-28827
Journal ID: ISSN 2469-9950; PRBMDO; 131765; TRN: US1702673
- Grant/Contract Number:
- AC02-06CH11357; AC52-06NA25396; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review B
- Additional Journal Information:
- Journal Volume: 95; Journal Issue: 13; Journal ID: ISSN 2469-9950
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; High Magnetic Field Science
Citation Formats
Brambleby, Jamie, Manson, Jamie L., Goddard, Paul A., Stone, Matthew B., Johnson, Roger D., Manuel, Pascal, Villa, Jacqueline A., Brown, Craig M., Lu, Helen, Chikara, Shalinee, Zapf, Vivien, Lapidus, Saul H., Scatena, Rebecca, Macchi, Piero, Chen, Yu-sheng, Wu, Lai -Chin, and Singleton, John. Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S=1 quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a S=1 quantum antiferromagnet]. United States: N. p., 2017.
Web. doi:10.1103/PhysRevB.95.134435.
Brambleby, Jamie, Manson, Jamie L., Goddard, Paul A., Stone, Matthew B., Johnson, Roger D., Manuel, Pascal, Villa, Jacqueline A., Brown, Craig M., Lu, Helen, Chikara, Shalinee, Zapf, Vivien, Lapidus, Saul H., Scatena, Rebecca, Macchi, Piero, Chen, Yu-sheng, Wu, Lai -Chin, & Singleton, John. Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S=1 quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a S=1 quantum antiferromagnet]. United States. https://doi.org/10.1103/PhysRevB.95.134435
Brambleby, Jamie, Manson, Jamie L., Goddard, Paul A., Stone, Matthew B., Johnson, Roger D., Manuel, Pascal, Villa, Jacqueline A., Brown, Craig M., Lu, Helen, Chikara, Shalinee, Zapf, Vivien, Lapidus, Saul H., Scatena, Rebecca, Macchi, Piero, Chen, Yu-sheng, Wu, Lai -Chin, and Singleton, John. Thu .
"Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S=1 quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a S=1 quantum antiferromagnet]". United States. https://doi.org/10.1103/PhysRevB.95.134435. https://www.osti.gov/servlets/purl/1373946.
@article{osti_1373946,
title = {Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S=1 quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a S=1 quantum antiferromagnet]},
author = {Brambleby, Jamie and Manson, Jamie L. and Goddard, Paul A. and Stone, Matthew B. and Johnson, Roger D. and Manuel, Pascal and Villa, Jacqueline A. and Brown, Craig M. and Lu, Helen and Chikara, Shalinee and Zapf, Vivien and Lapidus, Saul H. and Scatena, Rebecca and Macchi, Piero and Chen, Yu-sheng and Wu, Lai -Chin and Singleton, John},
abstractNote = {The magnetic ground state of the quasi-one-dimensional spin-1 antiferromagnetic chain is sensitive to the relative sizes of the single-ion anisotropy (D) and the intrachain (J) and interchain (J') exchange interactions. The ratios D/J and J' /J dictate the material's placement in one of three competing phases: a Haldane gapped phase, a quantum paramagnet, and an XY-ordered state, with a quantum critical point at their junction. We have identified [Ni(HF2)(pyz)2] SbF6, where pyz = pyrazine, as a rare candidate in which this behavior can be explored in detail. Combining neutron scattering (elastic and inelastic) in applied magnetic fields of up to 10 tesla and magnetization measurements in fields of up to 60 tesla with numerical modeling of experimental observables, we are able to obtain accurate values of all of the parameters of the Hamiltonian [D = 13.3(1) K, J = 10.4(3) K, and J' = 1.4(2) K], despite the polycrystalline nature of the sample. Density-functional theory calculations result in similar couplings (J = 9.2 K, J' = 1.8 K) and predict that the majority of the total spin population resides on the Ni(II) ion, while the remaining spin density is delocalized over both ligand types. Finally, the general procedures outlined in this paper permit phase boundaries and quantum-critical points to be explored in anisotropic systems for which single crystals are as yet unavailable.},
doi = {10.1103/PhysRevB.95.134435},
journal = {Physical Review B},
number = 13,
volume = 95,
place = {United States},
year = {2017},
month = {4}
}
Web of Science
Works referenced in this record:
Field-induced magnetic ordering in
journal, January 2004
- Paduan-Filho, A.; Gratens, X.; Oliveira, N. F.
- Physical Review B, Vol. 69, Issue 2
Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets
journal, February 2016
- Dos Santos, Leonardo H. R.; Lanza, Arianna; Barton, Alyssa M.
- Journal of the American Chemical Society, Vol. 138, Issue 7
Nonlinear Field Theory of Large-Spin Heisenberg Antiferromagnets: Semiclassically Quantized Solitons of the One-Dimensional Easy-Axis Néel State
journal, April 1983
- Haldane, F. D. M.
- Physical Review Letters, Vol. 50, Issue 15
Calorimetric Investigation of Phase Transitions Occurring in Molecule-Based Magnets †
journal, March 2006
- Sorai, Michio; Nakano, Motohiro; Miyazaki, Yuji
- Chemical Reviews, Vol. 106, Issue 3
A Spectroscopic Investigation of Magnetic Exchange Between Highly Anisotropic Spin Centers
journal, March 2011
- Boeer, Angelika B.; Barra, Anne-Laure; Chibotaru, Liviu F.
- Angewandte Chemie International Edition, Vol. 50, Issue 17
Direct Measurement of the Bose-Einstein Condensation Universality Class in at Ultralow Temperatures
journal, October 2008
- Yin, L.; Xia, J. S.; Zapf, V. S.
- Physical Review Letters, Vol. 101, Issue 18
Magnetic Polyoxometalates: Anisotropic Exchange Interactions in the Moiety of [(NaOH 2 )Co 3 (H 2 O)(P 2 W 15 O 56 ) 2 ] 17 -
journal, May 2005
- Clemente-Juan, Juan Modesto; Coronado, Eugenio; Gaita-Ariño, Alejandro
- Inorganic Chemistry, Vol. 44, Issue 10
Magnetic Structure and Exchange Interactions in Quasi-One-Dimensional MnCl 2 (urea) 2
journal, December 2015
- Manson, Jamie L.; Huang, Qing-zhen; Brown, Craig M.
- Inorganic Chemistry, Vol. 54, Issue 24
Characterizing the Haldane phase in quasi-one-dimensional spin-1 Heisenberg antiferromagnets
journal, December 2014
- Wierschem, Keola; Sengupta, Pinaki
- Modern Physics Letters B, Vol. 28, Issue 32
Challenges for Density Functional Theory
journal, December 2011
- Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
- Chemical Reviews, Vol. 112, Issue 1
Topology and Spin Polarization in Sheetlike Metal(II) Polymers: [ML 2 X 2 ] (M ˭ Mn, Fe, Co or Ni, L = Pyrimidine or Pyrazine and X = NCS or NCO)
journal, September 1999
- Lloret, Francesc; Julve, Miguel; Cano, Juan
- Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 334, Issue 1
Strong H···F Hydrogen Bonds as Synthons in Polymeric Quantum Magnets: Structural, Magnetic, and Theoretical Characterization of [Cu(HF 2 )(pyrazine) 2 ]SbF 6 , [Cu 2 F(HF)(HF 2 )(pyrazine) 4 ](SbF 6 ) 2 , and [CuAg(H 3 F 4 )(pyrazine) 5 ](SbF 6 ) 2
journal, May 2009
- Manson, Jamie L.; Schlueter, John A.; Funk, Kylee A.
- Journal of the American Chemical Society, Vol. 131, Issue 19
Quantum criticality
journal, February 2011
- Sachdev, Subir; Keimer, Bernhard
- Physics Today, Vol. 64, Issue 2
Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993
- Rodríguez-Carvajal, Juan
- Physica B: Condensed Matter, Vol. 192, Issue 1-2
Bose-Einstein Condensation of Nickel Spin Degrees of Freedom in
journal, February 2006
- Zapf, V. S.; Zocco, D.; Hansen, B. R.
- Physical Review Letters, Vol. 96, Issue 7
Presumption for a Quantum Energy Gap in the Quasi-One-Dimensional S = 1 Heisenberg Antiferromagnet Ni(C 2 H 8 N 2 ) 2 NO 2 (ClO 4 )
journal, April 1987
- Renard, J. P.; Verdaguer, M.; Regnault, L. P.
- Europhysics Letters (EPL), Vol. 3, Issue 8
Spin–Lattice Coupling in [Ni(HF 2 )(pyrazine) 2 ]SbF 6 Involving the HF 2 – Superexchange Pathway
journal, November 2016
- O’Neal, Kenneth R.; Holinsworth, Brian S.; Chen, Zhiguo
- Inorganic Chemistry, Vol. 55, Issue 23
Inelastic Neutron Scattering and Magnetic Susceptibilities of the Single-Molecule Magnets [Mn 4 O 3 X(OAc) 3 (dbm) 3 ] (X = Br, Cl, OAc, and F): Variation of the Anisotropy along the Series
journal, December 2000
- Andres, Hanspeter; Basler, Reto; Güdel, Hans-Ulrich
- Journal of the American Chemical Society, Vol. 122, Issue 50
Spin-State Energetics of Fe II Complexes - The Continuing Voyage Through the Density Functional Minefield : Spin-State Energetics of Fe
journal, August 2014
- Houghton, Benjamin J.; Deeth, Robert J.
- European Journal of Inorganic Chemistry, Vol. 2014, Issue 27
Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling
journal, March 2009
- Neese, Frank
- Coordination Chemistry Reviews, Vol. 253, Issue 5-6
Ordering, metastability and phase transitions in two-dimensional systems
journal, April 1973
- Kosterlitz, J M; Thouless, D J
- Journal of Physics C: Solid State Physics, Vol. 6, Issue 7, p. 1181-1203
Structural, Electronic, and Magnetic Properties of Quasi-1D Quantum Magnets [Ni(HF 2 )(pyz) 2 ]X (pyz = pyrazine; X = PF 6 – , SbF 6 – ) Exhibiting Ni-FHF-Ni and Ni-pyz-Ni Spin Interactions
journal, July 2011
- Manson, Jamie L.; Lapidus, Saul H.; Stephens, Peter W.
- Inorganic Chemistry, Vol. 50, Issue 13
Magnetic ground state of the two isostructual polymeric quantum magnets and investigated with neutron powder diffraction
journal, October 2015
- Brambleby, J.; Goddard, P. A.; Johnson, R. D.
- Physical Review B, Vol. 92, Issue 13
Antiferromagnetism in a Family of S = 1 Square Lattice Coordination Polymers NiX 2 (pyz) 2 (X = Cl, Br, I, NCS; pyz = Pyrazine)
journal, March 2016
- Liu, Junjie; Goddard, Paul A.; Singleton, John
- Inorganic Chemistry, Vol. 55, Issue 7
Dimensional crossover in spin-1 Heisenberg antiferromagnets: a quantum Monte Carlo study
journal, December 2012
- Wierschem, Keola; Sengupta, Pinaki
- Journal of Physics: Conference Series, Vol. 400, Issue 3
Inelastic neutron scattering and frequency-domain magnetic resonance studies of and single-molecule magnets
journal, May 2010
- Pieper, O.; Guidi, T.; Carretta, S.
- Physical Review B, Vol. 81, Issue 17
[Ni(HF 2 )(3-Clpy) 4 ]BF 4 (py = pyridine): Evidence for Spin Exchange Along Strongly Distorted F···H···F – Bridges in a One-Dimensional Polymeric Chain
journal, April 2012
- Manson, Jamie L.; Baldwin, Adora G.; Scott, Brian L.
- Inorganic Chemistry, Vol. 51, Issue 14
Long range order and metastability in two dimensional solids and superfluids. (Application of dislocation theory)
journal, June 1972
- Kosterlitz, J. M.; Thouless, D. J.
- Journal of Physics C: Solid State Physics, Vol. 5, Issue 11
Zero-field splitting in metal complexes
journal, May 2004
- Boča, Roman
- Coordination Chemistry Reviews, Vol. 248, Issue 9-10
quasi-one-dimensional spin waves in CrCl
journal, September 2013
- Stone, M. B.; Ehlers, G.; Granroth, G. E.
- Physical Review B, Vol. 88, Issue 10
Linear spin wave theory for single-Q incommensurate magnetic structures
journal, March 2015
- Toth, S.; Lake, B.
- Journal of Physics: Condensed Matter, Vol. 27, Issue 16
Continuum dynamics of the 1-D Heisenberg antiferromagnet: Identification with the O(3) nonlinear sigma model
journal, February 1983
- Haldane, F. D. M.
- Physics Letters A, Vol. 93, Issue 9
Dispersive magnetic excitations in the antiferromagnet
journal, April 2008
- Stone, M. B.; Lumsden, M. D.; Qiu, Y.
- Physical Review B, Vol. 77, Issue 13
Mixed-Valent Cobalt Spin Clusters: a Hexanuclear Complex and a One-Dimensional Coordination Polymer Comprised of Alternating Hepta- and Mononuclear Fragments
journal, October 2006
- Alley, Kerwyn G.; Bircher, Roland; Waldmann, Oliver
- Inorganic Chemistry, Vol. 45, Issue 22
Exchange Alternation and Single-ion Anisotropy in The Antiferromagnetic Heisenberg Chain S = 1. Magnetic and Thermal Properties of the Compound Ni2(EDTA).cntdot.6H2O
journal, May 1995
- Borras-Almenar, J. J.; Coronado, E.; Curely, J.
- Inorganic Chemistry, Vol. 34, Issue 10
Works referencing / citing this record:
Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
journal, January 2019
- Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
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
Determining the anisotropy and exchange parameters of polycrystalline spin-1 magnets
journal, September 2019
- Blackmore, W. J. A.; Brambleby, J.; Lancaster, T.
- New Journal of Physics, Vol. 21, Issue 9
Unusual Magnetic Response of an S = 1 Antiferromagetic Linear-Chain Material
journal, March 2018
- Xia, Jian-Sheng; Ozarowski, Andrzej; Spurgeon, Peter M.
- Journal of Physics: Conference Series, Vol. 969
Giant Pressure Dependence and Dimensionality Switching in a Metal-Organic Quantum Antiferromagnet
journal, September 2018
- Wehinger, B.; Fiolka, C.; Lanza, A.
- Physical Review Letters, Vol. 121, Issue 11
Near-ideal molecule-based Haldane spin chain
journal, January 2020
- Williams, Robert C.; Blackmore, William J. A.; Curley, Samuel P. M.
- Physical Review Research, Vol. 2, Issue 1
Giant Pressure Dependence and Dimensionality Switching in a Metal-Organic Quantum Antiferromagnet
text, January 2018
- Wehinger, B.; Fiolka, Christoph; Lanza, Arianna
- American Physical Society