Near-ideal molecule-based Haldane spin chain
Abstract
The molecular coordination complex [where (3,5-lut) (3,5-lutidine) )] has been synthesized and characterized by several techniques including synchrotron x-ray diffraction, electron-spin resonance, superconducting quantum interference device magnetometry, pulsed-field magnetization, inelastic neutron scattering, and muon spin relaxation. Templated by the configuration of 3,5-lut ligands the molecules pack in-registry with the Ni– –Ni chains aligned along the axis. This arrangement leads to an uncommon through-space magnetic coupling which is directly measured in this work. The net result is a near-ideal realization of the Haldane chain with and energy gaps of , split by the easy-axis single-ion anisotropy . The ratio affords one of the most isotropic Haldane systems yet discovered, while the ratio (where is the average gap size) is close to its ideal theoretical value, suggesting a very high degree of magnetic isolation of the spin chains in this material. The Haldane gap is closed by orientation-dependent critical fields and , which are readily accessible experimentally and permit investigations across the entirety of the Haldane phase, with the fully polarized state occurring at and . The results are explicable within the so-called fermion model, in contrast to other reported easy-axis Haldane systems. Zero-field magnetic order is absent down to and emergent end-chain effects are observed in the gapped state, as evidenced by detailed low-temperature measurements.
- Authors:
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); National Science Foundation (NSF); Engineering and Physical Sciences Research Council (EPSRC)
- OSTI Identifier:
- 1595175
- Alternate Identifier(s):
- OSTI ID: 1783522
- Report Number(s):
- LA-UR-19-27659
Journal ID: ISSN 2643-1564; PPRHAI; 013082
- Grant/Contract Number:
- AC02-06CH11357; 89233218CNA000001; DMR-1157490; DMR-1703003; CHE-1834750; EP/N023803/1; EP/N024028/1; EP/N032128/1
- Resource Type:
- Published Article
- Journal Name:
- Physical Review Research
- Additional Journal Information:
- Journal Name: Physical Review Research Journal Volume: 2 Journal Issue: 1; Journal ID: ISSN 2643-1564
- Publisher:
- American Physical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; High magnetic field science; quantum phase transitions; topological phases of matter; 1-dimensional spin chains
Citation Formats
Williams, Robert C., Blackmore, William J. A., Curley, Samuel P. M., Lees, Martin R., Birnbaum, Serena M., Singleton, John, Huddart, Benjamin M., Hicken, Thomas J., Lancaster, Tom, Blundell, Stephen J., Xiao, Fan, Ozarowski, Andrew, Pratt, Francis L., Voneshen, David J., Guguchia, Zurab, Baines, Christopher, Schlueter, John A., Villa, Danielle Y., Manson, Jamie L., and Goddard, Paul A.. Near-ideal molecule-based Haldane spin chain. United States: N. p., 2020.
Web. doi:10.1103/PhysRevResearch.2.013082.
Williams, Robert C., Blackmore, William J. A., Curley, Samuel P. M., Lees, Martin R., Birnbaum, Serena M., Singleton, John, Huddart, Benjamin M., Hicken, Thomas J., Lancaster, Tom, Blundell, Stephen J., Xiao, Fan, Ozarowski, Andrew, Pratt, Francis L., Voneshen, David J., Guguchia, Zurab, Baines, Christopher, Schlueter, John A., Villa, Danielle Y., Manson, Jamie L., & Goddard, Paul A.. Near-ideal molecule-based Haldane spin chain. United States. https://doi.org/10.1103/PhysRevResearch.2.013082
Williams, Robert C., Blackmore, William J. A., Curley, Samuel P. M., Lees, Martin R., Birnbaum, Serena M., Singleton, John, Huddart, Benjamin M., Hicken, Thomas J., Lancaster, Tom, Blundell, Stephen J., Xiao, Fan, Ozarowski, Andrew, Pratt, Francis L., Voneshen, David J., Guguchia, Zurab, Baines, Christopher, Schlueter, John A., Villa, Danielle Y., Manson, Jamie L., and Goddard, Paul A.. Mon .
"Near-ideal molecule-based Haldane spin chain". United States. https://doi.org/10.1103/PhysRevResearch.2.013082.
@article{osti_1595175,
title = {Near-ideal molecule-based Haldane spin chain},
author = {Williams, Robert C. and Blackmore, William J. A. and Curley, Samuel P. M. and Lees, Martin R. and Birnbaum, Serena M. and Singleton, John and Huddart, Benjamin M. and Hicken, Thomas J. and Lancaster, Tom and Blundell, Stephen J. and Xiao, Fan and Ozarowski, Andrew and Pratt, Francis L. and Voneshen, David J. and Guguchia, Zurab and Baines, Christopher and Schlueter, John A. and Villa, Danielle Y. and Manson, Jamie L. and Goddard, Paul A.},
abstractNote = {The molecular coordination complex NiI2(3,5-lut)4 [where (3,5-lut) = (3,5-lutidine) =(C7H9N)] has been synthesized and characterized by several techniques including synchrotron x-ray diffraction, electron-spin resonance, superconducting quantum interference device magnetometry, pulsed-field magnetization, inelastic neutron scattering, and muon spin relaxation. Templated by the configuration of 3,5-lut ligands the molecules pack in-registry with the Ni–I∙∙∙I–Ni chains aligned along the c axis. This arrangement leads to an uncommon through-space I∙∙∙I magnetic coupling which is directly measured in this work. The net result is a near-ideal realization of the S=1 Haldane chain with J=17.5K and energy gaps of Δ∥=5.3K Δ⊥=7.7K, split by the easy-axis single-ion anisotropy D=-1.2K. The ratio D/J=-0.07 affords one of the most isotropic Haldane systems yet discovered, while the ratio Δ0/J=0.40(1) (where Δ0 is the average gap size) is close to its ideal theoretical value, suggesting a very high degree of magnetic isolation of the spin chains in this material. The Haldane gap is closed by orientation-dependent critical fields μ0Hc∥=5.3T and μ0Hc⊥=4.3T, which are readily accessible experimentally and permit investigations across the entirety of the Haldane phase, with the fully polarized state occurring at μ0Hs∥=46.0T and μ0Hs⊥=50.7T. The results are explicable within the so-called fermion model, in contrast to other reported easy-axis Haldane systems. Zero-field magnetic order is absent down to 20mK and emergent end-chain effects are observed in the gapped state, as evidenced by detailed low-temperature measurements.},
doi = {10.1103/PhysRevResearch.2.013082},
journal = {Physical Review Research},
number = 1,
volume = 2,
place = {United States},
year = {2020},
month = {1}
}
https://doi.org/10.1103/PhysRevResearch.2.013082
Works referenced in this record:
Zone-boundary excitations in coupled Haldane spin chain compounds PbNi 2 V 2 O 8 and SrNi 2 V 2 O 8
journal, September 2001
- Zheludev, A.; Masuda, T.; Uchinokura, K.
- Physical Review B, Vol. 64, Issue 13
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
Rigorous results on valence-bond ground states in antiferromagnets
journal, August 1987
- Affleck, Ian; Kennedy, Tom; Lieb, Elliott H.
- Physical Review Letters, Vol. 59, Issue 7
μSR frequency spectra using the maximum entropy method
journal, December 1994
- Rainford, B. D.; Daniell, G. J.
- Hyperfine Interactions, Vol. 87, Issue 1
Continuum in the Spin-Excitation Spectrum of a Haldane Chain Observed by Neutron Scattering in
journal, June 2001
- Zaliznyak, I. A.; Lee, S. -H.; Petrov, S. V.
- Physical Review Letters, Vol. 87, Issue 1
Numerical renormalization-group study of low-lying eigenstates of the antiferromagnetic S =1 Heisenberg chain
journal, August 1993
- White, Steven R.; Huse, David A.
- Physical Review B, Vol. 48, Issue 6
Multiparticle States in the Chain System
journal, June 2001
- Kenzelmann, M.; Cowley, R. A.; Buyers, W. J. L.
- Physical Review Letters, Vol. 87, Issue 1
Static properties of the S =1 one-dimensional antiferromagnet
journal, November 1995
- Takigawa, M.; Asano, T.; Ajiro, Y.
- Physical Review B, Vol. 52, Issue 18
Impurities in s =1 Heisenberg antiferromagnets
journal, June 1995
- So/rensen, Erik S.; Affleck, Ian
- Physical Review B, Vol. 51, Issue 22
Effect of the Haldane gap on quasi-one-dimensional systems
journal, September 1990
- Sakai, Tôru; Takahashi, Minoru
- Physical Review B, Vol. 42, Issue 7
Dimensionality Selection in a Molecule-Based Magnet
journal, February 2012
- Goddard, Paul A.; Manson, Jamie L.; Singleton, John
- Physical Review Letters, Vol. 108, Issue 7
Dynamics of an anisotropic Haldane antiferromagnet in a strong magnetic field
journal, February 2004
- Zheludev, A.; Shapiro, S. M.; Honda, Z.
- Physical Review B, Vol. 69, Issue 5
Quantum criticality
journal, February 2011
- Sachdev, Subir; Keimer, Bernhard
- Physics Today, Vol. 64, Issue 2
Molecular magnets
journal, September 2007
- Blundell, Stephen J.
- Contemporary Physics, Vol. 48, Issue 5
Spectral function for the Heisenberg antiferromagetic chain
journal, April 2008
- White, Steven R.; Affleck, Ian
- Physical Review B, Vol. 77, Issue 13
Magnetic Spin Ladder ( C 5 H 12 N ) 2 Cu Br 4 : High-Field Magnetization and Scaling near Quantum Criticality
journal, May 2001
- Watson, B. C.; Kotov, V. N.; Meisel, M. W.
- Physical Review Letters, Vol. 86, Issue 22
The crystal and molecular structure of diiodotetrakis(pyridine)nickel(II) [Nipy4I2]
journal, January 1973
- Hamm, D. J.; Bordner, J.; Schreiner, A. F.
- Inorganica Chimica Acta, Vol. 7
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
Spin-Vacancy-Induced Long-Range Order in a New Haldane-Gap Antiferromagnet
journal, July 1999
- Uchiyama, Y.; Sasago, Y.; Tsukada, I.
- Physical Review Letters, Vol. 83, Issue 3
Quantum phase transitions driven by rhombic-type single-ion anisotropy in the Haldane chain
journal, August 2017
- Tzeng, Yu-Chin; Onishi, Hiroaki; Okubo, Tsuyoshi
- Physical Review B, Vol. 96, Issue 6
Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an quantum antiferromagnet
journal, April 2017
- Brambleby, Jamie; Manson, Jamie L.; Goddard, Paul A.
- Physical Review B, Vol. 95, Issue 13
Gap of the linear spin-1 Heisenberg antiferromagnet: A Monte Carlo calculation
journal, January 1986
- Nightingale, M. P.; Blöte, H. W. J.
- Physical Review B, Vol. 33, Issue 1
Cluster Algorithms for General- Quantum Spin Systems
journal, July 2001
- Todo, Synge; Kato, Kiyoshi
- Physical Review Letters, Vol. 87, Issue 4
Finite-lattice extrapolations for a Haldane-gap antiferromagnet
journal, August 1994
- Golinelli, O.; Jolicoeur, Th.; Lacaze, R.
- Physical Review B, Vol. 50, Issue 5
Theory of electron spin resonance in Haldane-gap antiferromagnets
journal, October 1992
- Affleck, Ian
- Physical Review B, Vol. 46, Issue 14
Spin dynamics of the anisotropic spin-1 antiferromagnetic chain at finite magnetic fields
journal, February 2015
- Rahnavard, Yousef; Brenig, Wolfram
- Physical Review B, Vol. 91, Issue 5
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
Superexchange interaction and symmetry properties of electron orbitals
journal, July 1959
- Kanamori, Junjiro
- Journal of Physics and Chemistry of Solids, Vol. 10, Issue 2-3
Magnetic properties of the Haldane-gap material [Ni(C 2 H 8 N 2 ) 2 NO 2 ](BF 4 )
journal, March 2008
- Čižmár, E.; Ozerov, M.; Ignatchik, O.
- New Journal of Physics, Vol. 10, Issue 3
Neutron Scattering Study of Magnetic Excitations in the Spin S = 1 One-Dimensional Heisenberg Antiferromagnet Y 2 B a N i O 5
journal, September 1996
- Sakaguchi, Takehiro; Kakurai, Kazuhisa; Yokoo, Tetsuya
- Journal of the Physical Society of Japan, Vol. 65, Issue 9
Magnetic order in the quasi-one-dimensional spin- molecular chain compound copper pyrazine dinitrate
journal, January 2006
- Lancaster, T.; Blundell, S. J.; Brooks, M. L.
- Physical Review B, Vol. 73, Issue 2
Consequences of critical interchain couplings and anisotropy on a Haldane chain
journal, April 2015
- Bera, A. K.; Lake, B.; Islam, A. T. M. N.
- Physical Review B, Vol. 91, Issue 14
Dynamics of paramagnets at zero temperature
journal, May 2007
- Farutin, A. M.; Marchenko, V. I.
- Journal of Experimental and Theoretical Physics, Vol. 104, Issue 5
Evidence of a magnetic Bose glass in from neutron diffraction
journal, February 2010
- Hong, Tao; Zheludev, A.; Manaka, H.
- Physical Review B, Vol. 81, Issue 6
Sensitive SQUID magnetometry for studying nanomagnetism
journal, April 2011
- Sawicki, M.; Stefanowicz, W.; Ney, A.
- Semiconductor Science and Technology, Vol. 26, Issue 6
NMR relaxation in the spin-1 Heisenberg chain
journal, September 2019
- Capponi, Sylvain; Dupont, Maxime; Sandvik, Anders W.
- Physical Review B, Vol. 100, Issue 9
Bose-Einstein condensation in quantum magnets
journal, May 2014
- Zapf, Vivien; Jaime, Marcelo; Batista, C. D.
- Reviews of Modern Physics, Vol. 86, Issue 2
Quasiparticle breakdown in a quantum spin liquid
journal, March 2006
- Stone, Matthew B.; Zaliznyak, Igor A.; Hong, Tao
- Nature, Vol. 440, Issue 7081
Padé approximations for the magnetic susceptibilities of Heisenberg antiferromagnetic spin chains for various spin values
journal, January 2013
- Law, J. M.; Benner, H.; Kremer, R. K.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 6
Critical properties of coupled anisotropic Haldane spin chains in a magnetic field
journal, August 2015
- Bera, A. K.; Lake, B.; Islam, A. T. M. N.
- Physical Review B, Vol. 92, Issue 6
Field-induced magnetic ordering and single-ion anisotropy in the quasi-one-dimensional Haldane chain compound SrNi 2 V 2 O 8 : A single-crystal investigation
journal, June 2013
- Bera, A. K.; Lake, B.; Islam, A. T. M. N.
- Physical Review B, Vol. 87, Issue 22
Triplet spin resonance of the Haldane magnet Pb Ni 2 V 2 O 8 with interchain coupling
journal, March 2008
- Smirnov, A. I.; Glazkov, V. N.; Kashiwagi, T.
- Physical Review B, Vol. 77, Issue 10
Dynamic structure factor [ S ( Q ,ω)] of the S =1 quasi-one-dimensional Heisenberg antiferromagnet: Neutron-scattering study on
journal, July 1991
- Mutka, H.; Payen, C.; Molinié, P.
- Physical Review Letters, Vol. 67, Issue 4
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
Bose glass and Mott glass of quasiparticles in a doped quantum magnet
journal, September 2012
- Yu, Rong; Yin, Liang; Sullivan, Neil S.
- Nature, Vol. 489, Issue 7416
Massive triplet excitations in a magnetized anisotropic Haldane spin chain
journal, October 2003
- Zheludev, A.; Honda, Z.; Broholm, C. L.
- Physical Review B, Vol. 68, Issue 13
Linear Magnetic Chains with Anisotropic Coupling
journal, August 1964
- Bonner, Jill C.; Fisher, Michael E.
- Physical Review, Vol. 135, Issue 3A
Field-Induced Tomonaga-Luttinger Liquid Phase of a Two-Leg Spin-1/2 Ladder with Strong Leg Interactions
journal, September 2010
- Hong, Tao; Kim, Y. H.; Hotta, C.
- Physical Review Letters, Vol. 105, Issue 13
Observation of S =1/2 degrees of freedom in an S =1 linear-chain Heisenberg antiferromagnet
journal, December 1990
- Hagiwara, M.; Katsumata, K.; Affleck, Ian
- Physical Review Letters, Vol. 65, Issue 25
Impurity state in the Haldane gap for an S = 1 Heisenberg antiferromagnetic chain with bond doping
journal, January 1996
- Wang, Xiaoqun; Mallwitz, Steffen
- Physical Review B, Vol. 53, Issue 2
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
Quantum magnetism in molecular spin ladders probed with muon-spin spectroscopy
journal, October 2018
- Lancaster, T.; Xiao, F.; Huddart, B. M.
- New Journal of Physics, Vol. 20, Issue 10
Quenching the Haldane Gap in Spin-1 Heisenberg Antiferromagnets
journal, June 2014
- Wierschem, Keola; Sengupta, Pinaki
- Physical Review Letters, Vol. 112, Issue 24
Dominance of long-lived excitations in the antiferromagnetic spin-1 chain NENP
journal, December 1992
- Ma, Shaolong; Broholm, Collin; Reich, Daniel H.
- Physical Review Letters, Vol. 69, Issue 24
High-field multifrequency electron-spin-resonance study of the Haldane magnet Ni ( C 5 H 14 N 2 ) 2 N 3 ( PF 6 )
journal, January 2009
- Kashiwagi, T.; Hagiwara, M.; Kimura, S.
- Physical Review B, Vol. 79, Issue 2
Haldane gaps in a spin-1 Heisenberg chain with easy-plane single-ion anisotropy
journal, May 1992
- Golinelli, O.; Jolicoeur, Th.; Lacaze, R.
- Physical Review B, Vol. 45, Issue 17
Spin-polarized muons in condensed matter physics
journal, May 1999
- Blundell, S. J.
- Contemporary Physics, Vol. 40, Issue 3
Field-theory treatment of the Heisenberg spin-1 chain
journal, December 1990
- Tsvelik, A. M.
- Physical Review B, Vol. 42, Issue 16
Sample size, position, and structure effects on magnetization measurements using second-order gradiometer pickup coils
journal, January 2006
- Stamenov, P.; Coey, J. M. D.
- Review of Scientific Instruments, Vol. 77, Issue 1
Inelastic-neutron-scattering study of the spin dynamics in the Haldane-gap system Ni( C 2 H 8 N 2 ) 2 NO 2 ClO 4
journal, October 1994
- Regnault, L. P.; Zaliznyak, I.; Renard, J. P.
- Physical Review B, Vol. 50, Issue 13
Dirty-boson physics with magnetic insulators
journal, October 2013
- Zheludev, Andrey; Roscilde, Tommaso
- Comptes Rendus Physique, Vol. 14, Issue 8
Possible Bose-Einstein condensate of magnons in single-crystalline
journal, April 2010
- Conner, B. S.; Zhou, H. D.; Jo, Y. J.
- Physical Review B, Vol. 81, Issue 13
Low-temperature magnetic measurements of an S =1 linear-chain Heisenberg antiferromagnet
journal, October 1992
- Avenel, O.; Xu, J.; Xia, J. S.
- Physical Review B, Vol. 46, Issue 13
The magnetic field behaviour of a Haldane-gap antiferromagnet
journal, October 1993
- Golinelli, O.; Jolicoeur, T.; Lacaze, R.
- Journal of Physics: Condensed Matter, Vol. 5, Issue 42
Thermodynamic properties of the Haldane spin chain: a statistical model for the elementary excitations
journal, December 1993
- Regnault, L. -P; Zaliznyak, I. A.; Meshkov, S. V.
- Journal of Physics: Condensed Matter, Vol. 5, Issue 50
Long symmetric high-pressure cell for magnetic measurements in superconducting quantum interference device magnetometer
journal, July 2006
- Kamenev, K. V.; Tancharakorn, S.; Robertson, N.
- Review of Scientific Instruments, Vol. 77, Issue 7
Zeeman Levels with Exotic Field Dependence in the High Field Phase of an S = 1 Heisenberg Antiferromagnetic Chain
journal, October 2003
- Hagiwara, M.; Honda, Z.; Katsumata, K.
- Physical Review Letters, Vol. 91, Issue 17
Magnetic excitations in coupled Haldane spin chains near the quantum critical point
journal, October 2000
- Zheludev, A.; Masuda, T.; Tsukada, I.
- Physical Review B, Vol. 62, Issue 13
WIMDA: a muon data analysis program for the Windows PC
journal, August 2000
- Pratt, F. L.
- Physica B: Condensed Matter, Vol. 289-290
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
Observation of fractional spin S =1/2 on open ends of S =1 linear antiferromagnetic chains: Nonmagnetic doping
journal, September 1991
- Glarum, S. H.; Geschwind, S.; Lee, K. M.
- Physical Review Letters, Vol. 67, Issue 12
Characterization of a quasi-one-dimensional spin-1/2 magnet which is gapless and paramagnetic for and
journal, January 1999
- Hammar, P. R.; Stone, M. B.; Reich, Daniel H.
- Physical Review B, Vol. 59, Issue 2
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
Y 2 BaNi O 5 : A nearly ideal realization of the S = 1 Heisenberg chain with antiferromagnetic interactions
journal, September 1996
- Xu, Guangyong; DiTusa, J. F.; Ito, T.
- Physical Review B, Vol. 54, Issue 10