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Title: Near-ideal molecule-based Haldane spin chain

Abstract

The molecular coordination complex NiI 2 ( 3 , 5 - lut ) 4 [where (3,5-lut) = (3,5-lutidine) = ( C 7 H 9 N )] 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 = 17.5 K and energy gaps of Δ = 5.3 K Δ = 7.7 K , split by the easy-axis single-ion anisotropy D = - 1.2 K . The ratio D / J = - 0.07 affords one of the most isotropic Haldane systems yet discovered, while the ratio Δ 0 / J = 0.40 ( 1 ) (where Δ 0 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 μ 0 H c = 5.3 T and μ 0 H c = 4.3 T , which are readily accessible experimentally and permit investigations across the entirety of the Haldane phase, with the fully polarized state occurring at μ 0 H s = 46.0 T and μ 0 H s = 50.7 T . 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 20 mK 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}
}

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