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Heterometallic spin-1/2 quantum magnet under hydrostatic pressure
Authors:
M. J. Coak,
D. Kamenskyi,
S. P. M. Curley,
B. M. Huddart,
J. P. Tidey,
A. Chmeruk,
T. Sakurai,
S. Okubo,
H. Ohta,
S. Kimura,
H. Nojiri,
D. Graf,
S. J. Clark,
Z. E. Manson,
J. L. Manson,
T. Lancaster,
P. A. Goddard
Abstract:
We investigate the properties of CuVOF$_4$(H$_2$O)$_6$$\cdot$H$_2$O, in which two different spin species, Cu(II) and V(IV), form antiferromagnetic spin-1/2 dimers with weak interdimer coupling provided via hydrogen bonding. Using radio-frequency susceptometry and electron-spin resonance (ESR), we show how the temperature-magnetic field spin-dimer phase diagram evolves as a function of applied hydr…
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We investigate the properties of CuVOF$_4$(H$_2$O)$_6$$\cdot$H$_2$O, in which two different spin species, Cu(II) and V(IV), form antiferromagnetic spin-1/2 dimers with weak interdimer coupling provided via hydrogen bonding. Using radio-frequency susceptometry and electron-spin resonance (ESR), we show how the temperature-magnetic field spin-dimer phase diagram evolves as a function of applied hydrostatic pressure and correlate this with pressure-induced changes to the crystal structure. These results, coupled with pressure-tuned DFT calculations, confirm the prior prediction that the primary exchange interaction is mediated via an unusual mechanism in which the V(IV) ions provide considerable spin density to the oxygen that joins the two spins in each dimer and which lies along the Jahn-Teller axis of the Cu(II) ion. In addition, the dissimilarity in the spins that make up each dimer unit leads to a non-linear field dependence of the electronic energy levels as detected in the ESR measurements.
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Submitted 13 May, 2026; v1 submitted 1 December, 2025;
originally announced December 2025.
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Single-ion anisotropy driven chiral magnetic order in a spin-1 antiferromagnetic chain
Authors:
S. Vaidya,
S. P. M. Curley,
P. Manuel,
J. Ross Stewart,
M. Duc Le,
A. Hernández-Melián,
T. J. Hicken,
C. Wang,
H. Luetkens,
J. Krieger,
S. J. Blundell,
T. Lancaster,
K. A. Wheeler,
D. Y. Villa,
Z. E. Manson,
J. A. Villa,
J. L. Manson,
J. Singleton,
R. D. Johnson,
P. A. Goddard
Abstract:
Chirality in magnetic systems gives rise to a wide range of exotic phenomena, yet its influence in $S=1$ chains remains largely unexplored. Here, we present a comprehensive experimental study of a chiral antiferromagnetic (AFM) $S=1$ chain, [Ni(pym)(H$_{2}$O)$_{4}$]SO$_{4} \cdot$ H$_{2}$O (pym = pyrimidine), where the Ni(II) octahedral orientation exhibits a four-fold chiral periodicity. Muon spin…
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Chirality in magnetic systems gives rise to a wide range of exotic phenomena, yet its influence in $S=1$ chains remains largely unexplored. Here, we present a comprehensive experimental study of a chiral antiferromagnetic (AFM) $S=1$ chain, [Ni(pym)(H$_{2}$O)$_{4}$]SO$_{4} \cdot$ H$_{2}$O (pym = pyrimidine), where the Ni(II) octahedral orientation exhibits a four-fold chiral periodicity. Muon spin rotation measurements indicate the onset of long-range magnetic order below $T_{\rm N} = 1.82(2)\,\mathrm{K}$. Neutron diffraction measurements reveal a chiral AFM order driven by a chiral modulation of the easy-axis anisotropy direction, rather than the typical scenario of Dzyaloshinskii-Moriya interactions, geometrical frustration or higher-order interactions. Inelastic neutron scattering (INS) measurements reveal dispersive spin-wave excitations well described by linear spin-wave theory, with Hamiltonian parameters $J_{0} = 6.81(1)\,\mathrm{K}$ (intrachain exchange), $J'_{1\rm a} = -0.091(1)\,\mathrm{K}$ (interchain exchange), and $D = -3.02(1)\,\mathrm{K}$ (easy-axis single-ion anisotropy). These parameters are further validated by Monte Carlo simulations of the magnetisation. Additionally, the INS data reveal multiple dispersionless bands, suggesting the presence of further excitations beyond the scope of our linear spin-wave theory.
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Submitted 8 September, 2025;
originally announced September 2025.
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Magnetic-field-induced ordering in a spin-1/2 chiral chain
Authors:
Rebecca Scatena,
Alberto Hernandez-Melian,
Benjamin M. Huddart,
Sam Curley,
Robert Williams,
Pascal Manuel,
Stephen J. Blundell,
Zurab Guguchia,
Zachary E. Manson,
Jamie L. Manson,
G. Timothy Noe,
John Singleton,
Tom Lancaster,
Paul A. Goddard,
Roger D. Johnson
Abstract:
We present neutron diffraction, muon spin rotation and pulsed-field magnetometry measurements on the Heisenberg quantum chiral chain [Cu(pym)(H2O)4]SiF6.H2O, which displays a four-fold-periodic rotation of the local environment around the Cu(II) S = 1/2 ions from site to site along the chain. Previous measurements on this material have shown the absence of magnetic order down to surprisingly low t…
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We present neutron diffraction, muon spin rotation and pulsed-field magnetometry measurements on the Heisenberg quantum chiral chain [Cu(pym)(H2O)4]SiF6.H2O, which displays a four-fold-periodic rotation of the local environment around the Cu(II) S = 1/2 ions from site to site along the chain. Previous measurements on this material have shown the absence of magnetic order down to surprisingly low temperatures >= 20 mK, as well as the presence of an energy gap for magnetic excitations that grows linearly with magnetic field. Here we find evidence at dilution refrigerator temperatures for a field-induced transition to long-range magnetic order above an applied magnetic field of 3 T. From the polarization of magnetic moments observed in applied fields we can identify the static magnetic structure that best accounts for the data. The proposed model is supported microscopically by the presence of an alternating component of the g tensor, which produces an internal two-fold staggered field that dictates both the direction of the ordered moments and the effective coupling between adjacent chains. The observed magnetic structure is contrary to previous proposals for the departure of the magnitude and field dependence of the energy gap from the predictions of the sine-Gordon model.
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Submitted 13 May, 2025;
originally announced May 2025.
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Magnetic properties of a staggered $S=1$ chain Ni(pym)(H$_{2}$O)$_{2}$(NO$_{3}$)$_{2}$ with an alternating single-ion anisotropy direction
Authors:
S. Vaidya,
S. P. M. Curley,
P. Manuel,
J. Ross Stewart,
M. Duc Le,
C. Balz,
T. Shiroka,
S. J. Blundell,
K. A. Wheeler,
I. Calderon-Lin,
Z. E. Manson,
J. L. Manson,
J. Singleton,
T. Lancaster,
R. D. Johnson,
P. A. Goddard
Abstract:
Materials composed of spin-1 antiferromagnetic (AFM) chains are known to adopt complex ground states which are sensitive to the single-ion-anisotropy (SIA) energy ($D$), and intrachain ($J_{0}$) and interchain ($J'_{i}$) exchange energy scales. While theoretical and experimental studies have extended this model to include various other energy scales, the effect of the lack of a common SIA axis is…
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Materials composed of spin-1 antiferromagnetic (AFM) chains are known to adopt complex ground states which are sensitive to the single-ion-anisotropy (SIA) energy ($D$), and intrachain ($J_{0}$) and interchain ($J'_{i}$) exchange energy scales. While theoretical and experimental studies have extended this model to include various other energy scales, the effect of the lack of a common SIA axis is not well explored. Here we investigate the magnetic properties of Ni(pyrimidine)(H$_{2}$O)$_{2}$(NO$_{3}$)$_{2}$, a chain compound where the tilting of Ni octahedra leads to a 2-fold alternation of the easy-axis directions along the chain. Muon-spin relaxation measurements indicate a transition to long-range order at $T_{\text{N}}=2.3$\,K and the magnetic structure is initially determined to be antiferromagnetic and collinear using elastic neutron diffraction experiments. Inelastic neutron scattering measurements were used to find $J_{0} = 5.107(7)$\,K, $D = 2.79(1)$\,K, $J'_{2}=0.18(3)$\,K and a rhombic anisotropy energy $E=0.19(9)$\,K. Mean-field modelling reveals that the ground state structure hosts spin canting of $φ\approx6.5^{\circ}$, which is not detectable above the noise floor of the elastic neutron diffraction data. Monte-Carlo simulation of the powder-averaged magnetization, $M(H)$, is then used to confirm these Hamiltonian parameters, while single-crystal $M(H)$ simulations provide insight into features observed in the data.
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Submitted 28 November, 2024; v1 submitted 25 July, 2024;
originally announced July 2024.
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Pseudo-easy-axis anisotropy in antiferromagnetic $S=1$ diamond-lattice systems Ni$X_{2}$(pym)$_{2}$
Authors:
S. Vaidya,
A. Hernández-Melián,
J. P. Tidey,
S. P. M. Curley,
S. Sharma,
P. Manuel,
C. Wang,
G. L. Hannaford,
S. J. Blundell,
Z. E. Manson,
J. L. Manson,
J. Singleton,
T. Lancaster,
R. D. Johnson,
P. A. Goddard
Abstract:
We investigate the magnetic properties of $S=1$ antiferromagnetic diamond lattice, Ni$X_{2}$(pyrimidine)$_{2}$ ($X$ = Cl, Br), hosting a single-ion anisotropy (SIA) orientation which alternates between neighbouring sites. Through neutron diffraction measurements of the $X$ = Cl compound, the ordered state spins are found to align collinearly along a pseudo-easy-axis, a unique direction created by…
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We investigate the magnetic properties of $S=1$ antiferromagnetic diamond lattice, Ni$X_{2}$(pyrimidine)$_{2}$ ($X$ = Cl, Br), hosting a single-ion anisotropy (SIA) orientation which alternates between neighbouring sites. Through neutron diffraction measurements of the $X$ = Cl compound, the ordered state spins are found to align collinearly along a pseudo-easy-axis, a unique direction created by the intersection of two easy planes. Similarities in the magnetization, exhibiting spin-flop transitions, and the magnetic susceptibility in the two compounds imply that the same magnetic structure and a pseudo-easy-axis is also present for $X$ = Br. We estimate the Hamiltonian parameters by combining analytical calculations and Monte-Carlo (MC) simulations of the spin-flop and saturation field. The MC simulations also reveal that the spin-flop transition occurs when the applied field is parallel to the pseudo-easy-axis. Contrary to conventional easy-axis systems, there exist field directions perpendicular to the pseudo-easy-axis for which the magnetic saturation is approached asymptotically and no symmetry-breaking phase transition is observed at finite fields.
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Submitted 28 November, 2024; v1 submitted 24 May, 2024;
originally announced May 2024.
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Asymmetric phase diagram and dimensional crossover in a system of spin-1/2 dimers under applied hydrostatic pressure
Authors:
M. J. Coak,
S. P. M. Curley,
Z. Hawkhead,
J. P. Tidey,
D. Graf,
S. J. Clark,
P. Sengupta,
Z. E. Manson,
T. Lancaster,
P. A. Goddard,
J. L. Manson
Abstract:
We present the magnetic and structural properties of [Cu(pyrazine)$_{0.5}$(glycine)]ClO$_4$ under applied pressure. As previously reported, at ambient pressure this material consists of quasi-two-dimensional layers of weakly coupled antiferromagnetic dimers which undergo Bose-Einstein condensation of triplet excitations between two magnetic field-induced quantum critical points (QCPs). The molecul…
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We present the magnetic and structural properties of [Cu(pyrazine)$_{0.5}$(glycine)]ClO$_4$ under applied pressure. As previously reported, at ambient pressure this material consists of quasi-two-dimensional layers of weakly coupled antiferromagnetic dimers which undergo Bose-Einstein condensation of triplet excitations between two magnetic field-induced quantum critical points (QCPs). The molecular building blocks from which the compound is constructed give rise to exchange strengths that are considerably lower than those found in other $S = 1/2$ dimer materials, which allows us to determine the pressure evolution of the entire field-temperature magnetic phase diagram using radio-frequency magnetometry. We find that a distinct phase emerges above the upper field-induced transition at elevated pressures and also show that an additional QCP is induced at zero-field at a critical pressure of $p_{\rm c} = 15.7(5)$ kbar. Pressure-dependent single-crystal X-ray diffraction and density functional theory calculations indicate that this QCP arises primarily from a dimensional crossover driven by an increase in the interdimer interactions between the planes. While the effect of quantum fluctuations on the lower field-induced transition is enhanced with applied pressure, quantum Monte Carlo calculations suggest that this alone cannot explain an unconventional asymmetry that develops in the phase diagram.
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Submitted 21 November, 2023; v1 submitted 24 August, 2023;
originally announced August 2023.
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Anomalous magnetic exchange in a dimerized quantum-magnet composed of unlike spin species
Authors:
S. P. M. Curley,
B. M. Huddart,
D. Kamenskyi,
M. J. Coak,
R. C. Williams,
S. Ghannadzadeh,
A. Schneider,
S. Okubo,
T. Sakurai,
J. P. Tidey,
D. Graf,
S. J. Clark,
S. J. Blundell,
F. L. Pratt,
M. T. F. Telling,
T. Lancaster,
J. L. Manson,
P. A. Goddard
Abstract:
We present here a study of the magnetic properties of the antiferromagnetic dimer material CuVOF$_4$(H$_2$O)$_6\cdot$H$_2$O, in which the dimer unit is composed of two different $S = 1/2$ species, Cu(II) and V(IV). An applied magnetic field of $μ_0H_{\rm c1} = 13.1(1)~\rm T$ is found to close the singlet-triplet energy gap, the magnitude of which is governed by the antiferromagnetic intradimer,…
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We present here a study of the magnetic properties of the antiferromagnetic dimer material CuVOF$_4$(H$_2$O)$_6\cdot$H$_2$O, in which the dimer unit is composed of two different $S = 1/2$ species, Cu(II) and V(IV). An applied magnetic field of $μ_0H_{\rm c1} = 13.1(1)~\rm T$ is found to close the singlet-triplet energy gap, the magnitude of which is governed by the antiferromagnetic intradimer, $J_0 \approx 21~\rm K$, and interdimer, $J' \approx 1~\rm K$, exchange energies, determined from magnetometry and electron-spin resonance measurements. The results of density functional theory (DFT) calculations are consistent with the experimental results and predicts antiferromagnetic coupling along all nearest-neighbor bonds, with the magnetic ground state comprising spins of different species aligning antiparallel to one another, while spins of the same species are aligned parallel. The magnetism in this system cannot be accurately described by the overlap between localized V orbitals and magnetic Cu orbitals lying in the Jahn-Teller (JT) plane, with a tight-binding model based on such a set of orbitals incorrectly predicting that interdimer exchange should be dominant. DFT calculations indicate significant spin density on the bridging oxide, suggesting instead an unusual mechanism in which intradimer exchange is mediated through the O atom on the Cu(II) JT axis.
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Submitted 7 September, 2021; v1 submitted 3 September, 2021;
originally announced September 2021.
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Magnetic ground-state of the one-dimensional ferromagnetic chain compounds $M$(NCS)$_2$(thiourea)$_2$; $M$ = Ni, Co
Authors:
Samuel P. M. Curley,
Rebecca Scatena,
Robert C. Williams,
Paul A. Goddard,
Piero Macchi,
Thomas J. Hicken,
Tom Lancaster,
Fan Xiao,
Stephen J. Blundell,
Vivien Zapf,
James C. Eckert,
Elizabeth H. Krenkel,
Jacqueline A. Villa,
Melissa L. Rhodehouse,
Jamie L. Manson
Abstract:
The magnetic properties of the two isostructural molecule-based magnets, Ni(NCS)$_{2}$(thiourea)$_{2}$, $S$ = 1, [thiourea = SC(NH$_2$)$_2$] and Co(NCS)$_{2}$(thiourea)$_{2}$, $S$ = 3/2, are characterised using several techniques in order to rationalise their relationship with structural parameters and ascertain magnetic changes caused by substitution of the spin. Zero-field heat capacity and muon…
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The magnetic properties of the two isostructural molecule-based magnets, Ni(NCS)$_{2}$(thiourea)$_{2}$, $S$ = 1, [thiourea = SC(NH$_2$)$_2$] and Co(NCS)$_{2}$(thiourea)$_{2}$, $S$ = 3/2, are characterised using several techniques in order to rationalise their relationship with structural parameters and ascertain magnetic changes caused by substitution of the spin. Zero-field heat capacity and muon-spin relaxation measurements reveal low-temperature long-range ordering in both compounds, in addition to Ising-like ($D < 0$) single-ion anisotropy ($D_{\rm{Co}} \sim$ -100 K, $D_{\rm{Ni}} \sim$ -10 K). Crystal and electronic structure, combined with DC-field magnetometry, affirm highly quasi-one-dimensional behaviour, with ferromagnetic intrachain exchange interactions $J_{\rm{Co}}\approx+4$ K and $J_{\rm{Ni}}\sim+100$ K and weak antiferromagnetic interchain exchange, on the order of $J'$ $\sim-0.1$ K. Electron charge and spin-density mapping reveals through-space exchange as a mechanism to explain the large discrepancy in $J$-values despite, from a structural perspective, the highly similar exchange pathways in both materials. Both species can be compared to the similar compounds $M$Cl$_2$(thiourea)$_4$, $M$ = Ni(II) (DTN) and Co(II) (DTC), where DTN is know to harbour two magnetic field-induced quantum critical points. Direct comparison of DTN and DTC with the compounds studied here shows that substituting the halide Cl$^-$ ion, for the NCS$^-$ ion, results in a dramatic change in both the structural and magnetic properties.
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Submitted 10 March, 2021; v1 submitted 1 December, 2020;
originally announced December 2020.
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Magnetic order and ballistic spin transport in a sine-Gordon spin chain
Authors:
B. M. Huddart,
M. Gomilšek,
T. J. Hicken,
F. L. Pratt,
S. J. Blundell,
P. A. Goddard,
S. J. Kaech,
J. L. Manson,
T. Lancaster
Abstract:
We report the results of muon-spin spectroscopy ($μ^+$SR) measurements on the staggered molecular spin chain [pym-Cu(NO$_3$)$_2$(H$_2$O)$_2$] (pym = pyrimidine), a material previously described using sine-Gordon field theory. Zero-field $μ^+$SR reveals a long range magnetically-ordered ground state below a transition temperature $T_\mathrm{N}=0.22(1)$ K. Using longitudinal-field (LF) $μ^+$SR we in…
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We report the results of muon-spin spectroscopy ($μ^+$SR) measurements on the staggered molecular spin chain [pym-Cu(NO$_3$)$_2$(H$_2$O)$_2$] (pym = pyrimidine), a material previously described using sine-Gordon field theory. Zero-field $μ^+$SR reveals a long range magnetically-ordered ground state below a transition temperature $T_\mathrm{N}=0.22(1)$ K. Using longitudinal-field (LF) $μ^+$SR we investigate the dynamic response in applied magnetic fields $0< B < 500$ mT and find evidence for ballistic spin transport. Our LF $μ^+$SR measurements on the chiral spin chain [Cu(pym)(H$_2$O)$_4$]SiF$_6 \cdot $H$_2$O instead demonstrate one-dimensional spin diffusion and the distinct spin transport in these two systems likely reflects differences in their magnetic excitations.
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Submitted 24 June, 2020;
originally announced June 2020.
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Inelastic neutron scattering study of the anisotropic $S = 1$ spin chain [Ni(HF$_2$)(3-Clpyridine)$_4$]BF$_4$
Authors:
Daniel M. Pajerowski,
Jamie L. Manson,
Jacek Herbrych,
Jesper Bendix,
Andrey P. Podlesnyak,
John M. Cain,
Mark W. Meisel
Abstract:
[Ni(HF$_2$)(3-Clpyridine)$_4$]BF$_4$ (NBCT) is a one-dimensional, $S = 1$ spin chain material that shows no magnetic neutron Bragg peaks down temperatures of 0.1 K. Previous work identified NBCT to be in the Haldane phase and near a quantum phase transition as a function of $D/J$ to the large-$D$ quantum paramagnet phase (QPM), where $D$ is the axial single-ion anisotropy and $J$ is the intrachain…
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[Ni(HF$_2$)(3-Clpyridine)$_4$]BF$_4$ (NBCT) is a one-dimensional, $S = 1$ spin chain material that shows no magnetic neutron Bragg peaks down temperatures of 0.1 K. Previous work identified NBCT to be in the Haldane phase and near a quantum phase transition as a function of $D/J$ to the large-$D$ quantum paramagnet phase (QPM), where $D$ is the axial single-ion anisotropy and $J$ is the intrachain superexchange. Herein, inelastic neutron scattering results are presented on partially deuterated, $^{11}$B enriched NBCT polycrystalline samples in zero magnetic field and down to temperatures of 0.3 K. Comparison to density matrix renormalization group calculations yields $D/J = 1.51$ and a significant rhombic single-ion anisotropy $E$ ($E/D \approx 0.03$, $E/J \approx 0.05$). These $D$, $J$, and $E$ values place NBCT in the large-$D$ QPM phase but precipitously near a quantum phase transition to a long-range ordered phase.
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Submitted 23 January, 2020;
originally announced January 2020.
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A Near-Ideal Molecule-Based Haldane Spin-Chain
Authors:
Robert C. Williams,
William J. A. Blackmore,
Samuel P. M. Curley,
Martin R. Lees,
Serena M. Birnbaum,
John Singleton,
Benjamin M. Huddart,
Thomas J. Hicken,
Tom Lancaster,
Stephen J. Blundell,
Fan Xiao,
Andrew Ozarowski,
Francis L. Pratt,
David J. Voneshen,
Zurab Guguchia,
Christopher Baines,
John A. Schlueter,
Danielle Y. Villa,
Jamie L. Manson,
Paul A. Goddard
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, ESR, SQUID magnetometry, pulsed-field magnetization, inelastic neutron scattering and muon spin relaxation. Templated by the configuration of 3,5-lut ligands the molecules pack in-registr…
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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, ESR, SQUID 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$\cdots$I--Ni chains aligned along the $c$--axis. This arrangement leads to through-space I$\cdots$I magnetic coupling which is directly measured for the first time in this work. The net result is a near-ideal realization of the $S = 1$ Haldane chain with $J = 17.5~\rm{K}$ and energy gaps of $Δ^{\parallel} = 5.3~{\rm K}$ $Δ^{\perp} =7.7~{\rm K}$, split by the easy-axis single-ion anisotropy $D=-1.2~{\rm K}$. 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 $μ_0H_{\rm c}^{\parallel} = 5.3~\rm{T}$ and $μ_0H_{\rm c}^{\perp} = 4.3~\rm{T}$, which are readily accessible experimentally and permit investigations across the entirety of the Haldane phase, with the fully polarized state occurring at $μ_0 H_{\rm s}^{\parallel}=46.0~\rm{T}$ and $μ_0 H_{\rm s}^{\perp}=50.7~\rm{T}$. 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 $20~{\rm mK}$ and emergent end-chain effects are observed in the gapped state, as evidenced by detailed low-temperature measurements.
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Submitted 17 September, 2019;
originally announced September 2019.
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Determining the anisotropy and exchange parameters of polycrystalline spin-1 magnets
Authors:
William J. A. Blackmore,
Jamie Brambleby,
Tom Lancaster,
Stewart J. Clark,
Roger D. Johnson,
John Singleton,
Andrew Ozarowski,
John A. Schlueter,
Yu-Shen Cheng,
Atta M. Arif,
Saul Lapidus,
Fan Xiao,
Robert C. Williams,
Stephen J. Blundell,
Matthew J. Pearce,
Martin R. Lees,
Pascal Manuel,
Danielle Y. Villa,
Jacqueline A. Villa,
Jamie L. Manson,
Paul A. Goddard
Abstract:
Although low-dimensional $S = 1$ antiferromagnets remain of great interest, difficulty in obtaining high-quality single crystals of the newest materials hinders experimental research in this area. Polycrystalline samples are more readily produced, but there are inherent problems in extracting the magnetic properties of anisotropic systems from powder data. Following a discussion of the effect of p…
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Although low-dimensional $S = 1$ antiferromagnets remain of great interest, difficulty in obtaining high-quality single crystals of the newest materials hinders experimental research in this area. Polycrystalline samples are more readily produced, but there are inherent problems in extracting the magnetic properties of anisotropic systems from powder data. Following a discussion of the effect of powder-averaging on various measurement techniques, we present a methodology to overcome this issue using thermodynamic measurements. In particular we focus on whether it is possible to characterise the magnetic properties of polycrystalline, anisotropic samples using readily available laboratory equipment. We test the efficacy of our method using the magnets [Ni(H$_{2}$O)$_{2}$(3,5-lutidine)$_{4}$](BF$_{4}$)$_{2}$ and Ni(H$_{2}$O)$_{2}$(acetate)$_{2}$(4-picoline)$_{2}$, which have negligible exchange interactions, as well as the antiferromagnet [Ni(H$_{2}$O)$_{2}$(pyrazine)$_{2}$](BF$_{4}$)$_{2}$, and show that we are able to extract the anisotropy parameters in each case. The results obtained from the thermodynamic measurements are checked against electron-spin resonance and neutron diffraction. We also present a density functional method, which incorporates spin-orbit coupling to estimate the size of the anisotropy in [Ni(H$_{2}$O)$_{2}$(pyrazine)$_{2}$](BF$_{4}$)$_{2}$.
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Submitted 24 June, 2019;
originally announced June 2019.
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Unconventional field-induced spin gap in an $S = 1/2$ chiral staggered chain
Authors:
J. Liu,
S. Kittaka,
R. D. Johnson,
T. Lancaster,
J. Singleton,
T. Sakakibara,
Y. Kohama,
J. van Tol,
A. Ardavan,
B. H. Williams,
S. J. Blundell,
Z. E. Manson,
J. L. Manson,
P. A. Goddard
Abstract:
We investigate the low-temperature magnetic properties of the molecule-based chiral spin chain [Cu(pym)(H$_2$O)$_4$]SiF$_6\cdot$H$_2$O (pym = pyrimidine). Electron-spin resonance, magnetometry and heat capacity measurements reveal the presence of staggered $g$ tensors, a rich low-temperature excitation spectrum, a staggered susceptibility and a spin gap that opens on the application of a magnetic…
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We investigate the low-temperature magnetic properties of the molecule-based chiral spin chain [Cu(pym)(H$_2$O)$_4$]SiF$_6\cdot$H$_2$O (pym = pyrimidine). Electron-spin resonance, magnetometry and heat capacity measurements reveal the presence of staggered $g$ tensors, a rich low-temperature excitation spectrum, a staggered susceptibility and a spin gap that opens on the application of a magnetic field. These phenomena are reminiscent of those previously observed in non-chiral staggered chains, which are explicable within the sine-Gordon quantum-field theory. In the present case, however, although the sine-Gordon model accounts well for the form of the temperature-dependence of the heat capacity, the size of the gap and its measured linear field dependence do not fit with the sine-Gordon theory as it stands. We propose that the differences arise due to additional terms in the Hamiltonian resulting from the chiral structure of [Cu(pym)(H$_2$O)$_4$]SiF$_6\cdot$H$_2$O, particularly a uniform Dzyaloshinskii-Moriya coupling and a four-fold periodic staggered field.
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Submitted 8 January, 2019;
originally announced January 2019.
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Quantum magnetism in molecular spin ladders probed with muon-spin spectroscopy
Authors:
T. Lancaster,
F. Xiao,
B. M. Huddart,
R. C. Williams,
F. L. Pratt,
S. J. Blundell,
S. J. Clark,
R. Scheuermann,
T. Goko,
S. Ward,
J. L. Manson,
Ch. Rüegg,
K. W. Krämer
Abstract:
We present the results of muon-spin spectroscopy ($μ^{+}$SR) measurements on the molecular spin ladder system (Hpip)$_{2}$CuBr$_{4(1-x)}$Cl$_{4x}$, [Hpip=(C$_{5}$H$_{12}$N)]. Using transverse field $μ^{+}$SR we are able to identify characteristic behaviour in each of the regions of the phase diagram of the $x=0$ strong-rung spin ladder system (Hpip)$_{2}$CuBr$_4$. Comparison of our results to thos…
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We present the results of muon-spin spectroscopy ($μ^{+}$SR) measurements on the molecular spin ladder system (Hpip)$_{2}$CuBr$_{4(1-x)}$Cl$_{4x}$, [Hpip=(C$_{5}$H$_{12}$N)]. Using transverse field $μ^{+}$SR we are able to identify characteristic behaviour in each of the regions of the phase diagram of the $x=0$ strong-rung spin ladder system (Hpip)$_{2}$CuBr$_4$. Comparison of our results to those of the dimer-based molecular magnet Cu(pyz)(gly)(ClO$_{4}$) shows several common features. We locate the crossovers in partially disordered (Hpip)$_{2}$CuBr$_{4(1-x)}$Cl$_{4x}$ ($x=0.05$), where a region of behaviour intermediate between quantum disordered and Luttinger liquid-like is identified. Our interpretation of the results incorporates an analysis of the probable muon stopping states in (Hpip)$_{2}$CuBr$_4$ based on density functional calculations and suggests how the muon plus its local distortion can lead to a local probe unit with good sensitivity to the magnetic state. Using longitudinal field $μ^{+}$SR we compare the dynamic response of the $x=1$ strong-rung material (Hpip)$_{2}$CuCl$_{4}$ to that of the strong-leg material (C$_{7}$H$_{10}$N)$_{2}$CuBr$_{4}$ (known as DIMPY) and demonstrate that our results are in agreement with predictions based on interacting fermionic quasiparticle excitations in these materials.
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Submitted 25 June, 2018;
originally announced June 2018.
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Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a $S = 1$ quantum antiferromagnet
Authors:
Jamie Brambleby,
Jamie L. Manson,
Paul A. Goddard,
Matthew B. Stone,
Roger D. Johnson,
Pascal Manuel,
Jacqueline A. Villa,
Craig M. Brown,
Helen Lu,
Shalinee Chikara,
Vivien Zapf,
Saul H. Lapidus,
Rebecca Scatena,
Piero Macchi,
Yu-sheng Chen,
Lai-Chin Wu,
John Singleton
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 or other of three competing phases: a Haldane gapped phase, a quantum paramagnet and an XY-ordered state,…
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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 or other 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(HF)$_2$(pyz)$_2]$SbF$_6$, where pyz = pyrazine, as a 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 of resides on the Ni(II) ion, while the remaining spin density is delocalized over both ligand types. 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.
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Submitted 21 November, 2016;
originally announced November 2016.
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Adiabatic physics of an exchange-coupled spin-dimer system: magnetocaloric effect, zero-point fluctuations, and possible two-dimensional universal behavior
Authors:
J. Brambleby,
P. A. Goddard,
J. Singleton,
M. Jaime,
T. Lancaster,
L. Huang,
J. Wosnitza,
C. V. Topping,
K. E. Carreiro,
H. E. Tran,
Z. E. Manson,
J. L. Manson
Abstract:
We present the magnetic and thermal properties of the bosonic-superfluid phase in a spin-dimer network using both quasistatic and rapidly-changing pulsed magnetic fields. The entropy derived from a heat-capacity study reveals that the pulsed-field measurements are strongly adiabatic in nature and are responsible for the onset of a significant magnetocaloric effect (MCE). In contrast to previous pr…
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We present the magnetic and thermal properties of the bosonic-superfluid phase in a spin-dimer network using both quasistatic and rapidly-changing pulsed magnetic fields. The entropy derived from a heat-capacity study reveals that the pulsed-field measurements are strongly adiabatic in nature and are responsible for the onset of a significant magnetocaloric effect (MCE). In contrast to previous predictions we show that the MCE is not just confined to the critical regions, but occurs for all fields greater than zero at sufficiently low temperatures. We explain the MCE using a model of the thermal occupation of exchange-coupled dimer spin-states and highlight that failure to take this effect into account inevitably leads to incorrect interpretations of experimental results. In addition, the heat capacity in our material is suggestive of an extraordinary contribution from zero-point fluctuations and appears to indicate universal behavior with different critical exponents at the two field-induced critical points. The data are consistent with a two-dimensional nature of spin excitations in the system.
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Submitted 6 January, 2017; v1 submitted 27 October, 2016;
originally announced October 2016.
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Control of the third dimension in copper-based square-lattice antiferromagnets
Authors:
Paul A. Goddard,
John Singleton,
Isabel Franke,
Johannes S. Moller,
Tom Lancaster,
Andrew J. Steele,
Craig V. Topping,
Stephen J. Blundell,
Francis L. Pratt,
C. Baines,
Jesper Bendix,
Ross D. McDonald,
Jamie Brambleby,
Martin R. Lees,
Saul H. Lapidus,
Peter W. Stephens,
Brendan W. Twamley,
Marianne M. Conner,
Kylee Funk,
Jordan F. Corbey,
Hope E. Tran,
J. A. Schlueter,
Jamie L. Manson
Abstract:
Using a mixed-ligand synthetic scheme, we create a family of quasi-two-dimensional antiferromagnets, namely, [Cu(HF$_2$)(pyz)$_2$]ClO$_4$ [pyz = pyrazine], [Cu$L_2$(pyz)$_2$](ClO$_4$)$_2$ [$L$ = pyO = pyridine-N-oxide and 4-phpyO = 4-phenylpyridine-N-oxide. These materials are shown to possess equivalent two-dimensional [Cu(pyz)$_2$]$^{2+}$ nearly square layers, but exhibit interlayer spacings tha…
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Using a mixed-ligand synthetic scheme, we create a family of quasi-two-dimensional antiferromagnets, namely, [Cu(HF$_2$)(pyz)$_2$]ClO$_4$ [pyz = pyrazine], [Cu$L_2$(pyz)$_2$](ClO$_4$)$_2$ [$L$ = pyO = pyridine-N-oxide and 4-phpyO = 4-phenylpyridine-N-oxide. These materials are shown to possess equivalent two-dimensional [Cu(pyz)$_2$]$^{2+}$ nearly square layers, but exhibit interlayer spacings that vary from 6.5713~Å~to 16.777~Å, as dictated by the axial ligands. We present the structural and magnetic properties of this family as determined via x-ray diffraction, electron-spin resonance, pulsed- and quasistatic-field magnetometry and muon-spin rotation, and compare them to those of the prototypical two-dimensional magnetic polymer Cu(pyz)$_2$(ClO$_4$)$_2$. We find that, within the limits of the experimental error, the two-dimensional, {\it intralayer} exchange coupling in our family of materials remains largely unaffected by the axial ligand substitution, while the observed magnetic ordering temperature decreases slowly with increasing layer separation. Despite the structural motifs common to this family and Cu(pyz)$_2$(ClO$_4$)$_2$, the latter has significantly stronger two-dimensional exchange interactions and hence a higher ordering temperature. We discuss these results, as well as the mechanisms that might drive the long-range order in these materials, in terms of departures from the ideal $S=1/2$ two-dimensional square-lattice Heisenberg antiferromagnet. In particular, we find that both spin exchange anisotropy in the intralayer interaction and interlayer couplings (exchange, dipolar, or both) are needed to account for the observed ordering temperatures, with the intralayer anisotropy becoming more important as the layers are pulled further apart.
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Submitted 1 March, 2016;
originally announced March 2016.
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The magnetic ground state of two isostructual polymeric quantum magnets, [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ and [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, investigated with neutron powder diffraction
Authors:
J. Brambleby,
P. A. Goddard,
R. D. Johnson,
J. Liu,
D. Kaminski,
A. Ardavan,
A. J. Steele,
T. Lancaster,
P. Manuel,
P. J. Baker,
J. Singleton,
S. G. Schwalbe,
P. M. Spurgeon,
H. E. Tran,
P. K. Peterson,
J. F. Corbey,
J. L. Manson
Abstract:
The magnetic ground state of two isostructural coordination polymers (i) the quasi two-dimensional S = 1/2 square-lattice antiferromagnet [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$; and (ii) a new compound [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, were examined with neutron powder diffraction measurements. We find the ordered moments of the Heisenberg S = 1/2 Cu(II) ions in [Cu(HF$_{2}$)(pyrazine)…
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The magnetic ground state of two isostructural coordination polymers (i) the quasi two-dimensional S = 1/2 square-lattice antiferromagnet [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$; and (ii) a new compound [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, were examined with neutron powder diffraction measurements. We find the ordered moments of the Heisenberg S = 1/2 Cu(II) ions in [Cu(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ are 0.6(1)$μ_{B}$, whilst the ordered moments for the Co(II) ions in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ are 3.02(6)$μ_{B}$. For Cu(II), this reduced moment indicates the presence of quantum fluctuations below the ordering temperature. We show from heat capacity and electron spin resonance measurements, that due to the crystal electric field splitting of the S = 3/2 Co(II) ions in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$, this isostructual polymer also behaves as an effective spin-half magnet at low temperatures. The Co moments in [Co(HF$_{2}$)(pyrazine)$_{2}$]SbF$_{6}$ show strong easy-axis anisotropy, neutron diffraction data which do not support the presence of quantum fluctuations in the ground state and heat capacity data which are consistent with 2D or close to 3D spatial exchange anisotropy.
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Submitted 4 September, 2015; v1 submitted 29 May, 2015;
originally announced May 2015.
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Magnetism in a family of $S = 1$ square lattice antiferromagnets Ni$X_2$(pyz)$_2$ ($X = $ Cl, Br, I, NCS; pyz = pyrazine)
Authors:
J. Liu,
P. A. Goddard,
J. Singleton,
J. Brambleby,
F. Foronda,
J. S. Möller,
Y. Kohama,
S. Ghannadzadeh,
A. Ardavan,
S. J. Blundell,
T. Lancaster,
F. Xiao,
R. C. Williams,
F. L. Pratt,
P. J. Baker,
K. Wierschem,
S. H. Lapidus,
K. H. Stone,
P. W. Stephens,
J. Bendix,
M. R. Lees,
T. J. Woods,
K. E. Carreiro,
H. E. Tran,
C. J. Villa
, et al. (1 additional authors not shown)
Abstract:
The crystal structures of Ni$X_2$(pyz)$_2$ ($X$ = Cl (\textbf{1}), Br (\textbf{2}), I (\textbf{3}) and NCS (\textbf{4})) were determined at 298~K by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN$_4$$X_2$ units that are bridged by pyz ligands. The 2D layered motifs displayed by \textbf{1}-\textbf{4} are rele…
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The crystal structures of Ni$X_2$(pyz)$_2$ ($X$ = Cl (\textbf{1}), Br (\textbf{2}), I (\textbf{3}) and NCS (\textbf{4})) were determined at 298~K by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN$_4$$X_2$ units that are bridged by pyz ligands. The 2D layered motifs displayed by \textbf{1}-\textbf{4} are relevant to bifluoride-bridged [Ni(HF$_2$)(pyz)$_2$]$Z$F$_6$ ($Z$ = P, Sb) which also possess the same 2D layers. In contrast, terminal $X$ ligands occupy axial positions in \textbf{1}-\textbf{4} and cause a staggering of adjacent layers. Long-range antiferromagnetic order occurs below 1.5 (Cl), 1.9 (Br and NCS) and 2.5~K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and $g$ factor of \textbf{2}, \textbf{3} and \textbf{4} are measured by electron spin resonance where no zero--field splitting was found. The magnetism of \textbf{1}-\textbf{4} crosses a spectrum from quasi-two-dimensional to three-dimensional antiferromagnetism. An excellent agreement was found between the pulsed-field magnetization, magnetic susceptibility and $T_\textrm{N}$ of \textbf{2} and \textbf{4}. Magnetization curves for \textbf{2} and \textbf{4} calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. \textbf{3} is characterized as a three-dimensional antiferromagnet with the interlayer interaction ($J_\perp$) slightly stronger than the interaction within the two-dimensional [Ni(pyz)$_2$]$^{2+}$ square planes ($J_\textrm{pyz}$).
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Submitted 23 June, 2015; v1 submitted 12 October, 2014;
originally announced October 2014.
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Unusual Magnetic Response of an $S = 1$ Antiferromagetic Linear-Chain Material
Authors:
Jian-Sheng Xia,
Andrzej Ozarowski,
Peter M. Spurgeon,
Adora G. Baldwin,
Jamie L. Manson,
Mark W. Meisel
Abstract:
An $S=1$ antiferromagnetic polymeric chain, [Ni(HF$_2$)(3-Clpy)$_4$]BF$_4$ (py = pyridine), has previously been identified to have intrachain, nearest-neighbor antiferromagnetic interaction strength $J/k_{\mathrm{B}} = 4.86$ K and single-ion anisotropy (zero-field splitting) $D/k_{\mathrm{B}} = 4.3$ K, so the ratio $D/J = 0.88$ places this system close to the $D/J \approx 1$ gapless critical point…
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An $S=1$ antiferromagnetic polymeric chain, [Ni(HF$_2$)(3-Clpy)$_4$]BF$_4$ (py = pyridine), has previously been identified to have intrachain, nearest-neighbor antiferromagnetic interaction strength $J/k_{\mathrm{B}} = 4.86$ K and single-ion anisotropy (zero-field splitting) $D/k_{\mathrm{B}} = 4.3$ K, so the ratio $D/J = 0.88$ places this system close to the $D/J \approx 1$ gapless critical point between the topologically distinct Haldane and Large-$D$ phases. The magnetization was studied over a range of temperatures, 50 mK $\leq T \leq 1$ K, and magnetic fields, $B \leq 10$ T, in an attempt to identify a critical field, $B_{\mathrm{c}}$, associated with the closing of the Haldane gap, and the present work places an upper bound of $B_{\mathrm{c}} \leq (35 \pm 10)$ mT. At higher fields, the observed magnetic response is qualitatively similar to the "excess" signal observed by other workers at 0.5 K and below 3 T. The high-field (up to 14.5 T), multi-frequency (nomially 200 GHz to 425 GHz) ESR spectra at 3 K reveal several broad features considered to be associated with the linear-chain sample.
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Submitted 21 September, 2014;
originally announced September 2014.
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Spin diffusion in the low-dimensional molecular quantum Heisenberg antiferromagnet Cu(pyz)(NO$_{3}$)$_{2}$ detected with implanted muons
Authors:
F. Xiao,
J. S. Möller,
T. Lancaster,
R. C. Williams,
F. L. Pratt,
S. J. Blundell,
D. Ceresoli,
A. M. Barton,
J. L. Manson
Abstract:
We present the results of muon-spin relaxation measurements of spin excitations in the one-dimensional quantum Heisenberg antiferromagnet Cu(pyz)(NO$_{3}$)$_{2}$. Using density-functional theory we propose muon sites and assess the degree of perturbation the muon probe causes on the system. We identify a site involving the muon forming a hydroxyl-type bond with an oxygen on the nitrate group that…
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We present the results of muon-spin relaxation measurements of spin excitations in the one-dimensional quantum Heisenberg antiferromagnet Cu(pyz)(NO$_{3}$)$_{2}$. Using density-functional theory we propose muon sites and assess the degree of perturbation the muon probe causes on the system. We identify a site involving the muon forming a hydroxyl-type bond with an oxygen on the nitrate group that is sensitive to the characteristic spin dynamics of the system. Our measurements of the spin dynamics show that in the temperature range $T_{\mathrm{N}}<T<J$ (between the ordering temperature $T_{\mathrm{N}}$ and the exchange energy scale $J$) the field-dependent muon spin relaxation is characteristic of diffusive transport of spin excitations over a wide range of applied fields. We also identify a possible crossover at higher applied fields in the muon probe's response to the fluctuation spectrum, to a regime where the muon detects early-time transport with a ballistic character. This behavior is contrasted with that found for $T>J$ and that in the related two-dimensional system Cu(pyz)$_2$(ClO$_4$)$_{2}$.
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Submitted 2 April, 2015; v1 submitted 12 June, 2014;
originally announced June 2014.
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Controlling magnetic order and quantum disorder in one- and zero-dimensional molecule-based magnets
Authors:
T. Lancaster,
P. A. Goddard,
S. J. Blundell,
F. R. Foronda,
S. Ghannadzadeh,
J. S. Möller,
P. J. Baker,
F. L. Pratt,
C. Baines,
L. Huang,
J. Wosnitza,
R. D. McDonald,
K. A. Modic,
J. Singleton,
C. V. Topping,
T. A. W. Beale,
F. Xiao,
J. A. Schlueter,
R. D. Cabrera,
K. E. Carreiro,
H. E. Tran,
J. L. Manson
Abstract:
We investigate the structural and magnetic properties of two molecule-based magnets synthesized from the same starting components. Their different structural motifs promote contrasting exchange pathways and consequently lead to markedly different magnetic ground states. Through examination of their structural and magnetic properties we show that [Cu(pyz)(H$_{2}$O)(gly)$_{2}$](ClO$_{4}$)$_{2}$ may…
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We investigate the structural and magnetic properties of two molecule-based magnets synthesized from the same starting components. Their different structural motifs promote contrasting exchange pathways and consequently lead to markedly different magnetic ground states. Through examination of their structural and magnetic properties we show that [Cu(pyz)(H$_{2}$O)(gly)$_{2}$](ClO$_{4}$)$_{2}$ may be considered a quasi-one-dimensional quantum Heisenberg antiferromagnet while the related compound [Cu(pyz)(gly)](ClO$_{4}$), which is formed from dimers of antiferromagnetically interacting Cu$^{2+}$ spins, remains disordered down to at least 0.03 K in zero field, but shows a field-temperature phase diagram reminiscent of that seen in materials showing a Bose-Einstein condensation of magnons.
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Submitted 29 November, 2013;
originally announced November 2013.
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Evolution of magnetic interactions in a pressure-induced Jahn-Teller driven magnetic dimensionality switch
Authors:
S. Ghannadzadeh,
J. S. Möller,
P. A. Goddard,
T. Lancaster,
F. Xiao,
S. J. Blundell,
A. Maisuradze,
R. Khasanov,
J. L. Manson,
S. W. Tozer,
D. Graf,
J. A. Schlueter
Abstract:
We present the results of high-field magnetization and muon-spin relaxation measurements on the coordination polymer CuF_2(H_2O)_2(pyrazine) in pressures up to 22.5 kbar. We observe a transition from a quasi-two-dimensional to a quasi-one-dimensional antiferromagnetic phase at 9.1 kbar, driven by a rotation of the Jahn-Teller axis. Long-range antiferromagnetic ordering is seen in both regimes, as…
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We present the results of high-field magnetization and muon-spin relaxation measurements on the coordination polymer CuF_2(H_2O)_2(pyrazine) in pressures up to 22.5 kbar. We observe a transition from a quasi-two-dimensional to a quasi-one-dimensional antiferromagnetic phase at 9.1 kbar, driven by a rotation of the Jahn-Teller axis. Long-range antiferromagnetic ordering is seen in both regimes, as well as a phase separation in the critical pressure region. The magnetic dimensionality switching as pressure is increased is accompanied by a halving of the primary magnetic exchange energy J and a fivefold decrease in the ordering temperature T_N. J decreases gradually with pressure in the two-dimensional phase, and then increases in the one-dimensional regime. We relate both effects to the changes in the crystal structure with applied pressure.
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Submitted 19 April, 2013;
originally announced April 2013.
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Magnetic properties of the S=1/2 quasi square lattice antiferromagnet CuF2(H2O)2(pyz) (pyz=pyrazine) investigated by neutron scattering
Authors:
C. H. Wang,
M. D. Lumsden,
R. S. Fishman,
G. Ehlers,
T. Hong,
W. Tian,
H. Cao,
A. Podlesnyak,
C. Dunmars,
J. A. Schlueter,
J. L. Manson,
A. D. Christianson
Abstract:
We have performed elastic and inelastic neutron experiments on single crystal samples of the coordination polymer compound CuF2(H2O)2(pyz) (pyz=pyrazine) to study the magnetic structure and excitations. The elastic neutron diffraction measurements indicate a collinear antiferromagnetic structure with moments oriented along the [0.7 0 1] real-space direction and an ordered moment of 0.60 +/- 0.03 m…
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We have performed elastic and inelastic neutron experiments on single crystal samples of the coordination polymer compound CuF2(H2O)2(pyz) (pyz=pyrazine) to study the magnetic structure and excitations. The elastic neutron diffraction measurements indicate a collinear antiferromagnetic structure with moments oriented along the [0.7 0 1] real-space direction and an ordered moment of 0.60 +/- 0.03 muB/Cu. This value is significantly smaller than the single ion magnetic moment, reflecting the presence of strong quantum fluctuations. The spin wave dispersion from magnetic zone center to the zone boundary points (0.5 1.5 0) and (0.5 0 1.5) can be described by a two dimensional Heisenberg model with a nearest neighbor magnetic exchange constant J2d = 0.934 +/-0.0025 meV. The inter-layer interaction Jperp in this compound is less than 1.5% of J2d. The spin excitation energy at the (0.5 0.5 0.5) zone boundary point is reduced when compared to the (0.5 1 0.5) zone boundary point by ~10.3 +/- 1.4 %. This zone boundary dispersion is consistent with quantum Monte Carlo and series expansion calculations which include corrections for quantum fluctuations to linear spin wave theory.
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Submitted 15 August, 2012;
originally announced August 2012.
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Dimensionality selection in a molecule-based magnet
Authors:
Paul A. Goddard,
Jamie L. Manson,
John Singleton,
Isabel Franke,
Tom Lancaster,
Andrew J. Steele,
Stephen J. Blundell,
Christopher Baines,
Francis L. Pratt,
Ross D. McDonald,
Oscar E. Ayala-Valenzuela,
Jordan F. Corbey,
Heather I. Southerland,
Pinaki Sengupta,
John A. Schlueter
Abstract:
Gaining control of the building blocks of magnetic materials and thereby achieving particular characteristics will make possible the design and growth of bespoke magnetic devices. While progress in the synthesis of molecular materials, and especially coordination polymers, represents a significant step towards this goal, the ability to tune the magnetic interactions within a particular framework r…
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Gaining control of the building blocks of magnetic materials and thereby achieving particular characteristics will make possible the design and growth of bespoke magnetic devices. While progress in the synthesis of molecular materials, and especially coordination polymers, represents a significant step towards this goal, the ability to tune the magnetic interactions within a particular framework remains in its infancy. Here we demonstrate a chemical method which achieves dimensionality selection via preferential inhibition of the magnetic exchange in an $S=1/2$ antiferromagnet along one crystal direction, switching the system from being quasi-two- to quasi-one-dimensional while effectively maintaining the nearest-neighbour coupling strength.
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Submitted 27 January, 2012;
originally announced January 2012.
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Magnetic order in quasi-two-dimensional molecular magnets investigated with muon-spin relaxation
Authors:
Andrew J. Steele,
Tom Lancaster,
Stephen J. Blundell,
Peter J. Baker,
Francis L. Pratt,
Chris Baines,
Marianne M. Conner,
Heather I. Southerland,
Jamie L. Manson,
John A. Schlueter
Abstract:
We present the results of a muon-spin relaxation (muSR) investigation into magnetic ordering in several families of layered quasi-two-dimensional molecular antiferromagnets based on transition metal ions such as S=1/2 Cu2+ bridged with organic ligands such as pyrazine. In many of these materials magnetic ordering is difficult to detect with conventional magnetic probes. In contrast, muSR allows us…
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We present the results of a muon-spin relaxation (muSR) investigation into magnetic ordering in several families of layered quasi-two-dimensional molecular antiferromagnets based on transition metal ions such as S=1/2 Cu2+ bridged with organic ligands such as pyrazine. In many of these materials magnetic ordering is difficult to detect with conventional magnetic probes. In contrast, muSR allows us to identify ordering temperatures and study the critical behavior close to T_N . Combining this with measurements of in-plane magnetic exchange J and predictions from quantum Monte Carlo simulations we may assess the degree of isolation of the 2D layers through estimates of the effective inter-layer exchange coupling and in-layer correlation lengths at T_N . We also identify the likely metal-ion moment sizes and muon stopping sites in these materials, based on probabilistic analysis of the magnetic structures and of muon-fluorine dipole-dipole coupling in fluorinated materials.
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Submitted 25 August, 2011; v1 submitted 18 April, 2011;
originally announced April 2011.
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Experimental realization of field-induced XY and Ising ground states in a quasi-2D S=1/2 Heisenberg antiferromagnet
Authors:
Yoshimitsu Kohama. Marcelo Jaime,
Oscar E. Ayala-Valenzuela,
Ross D. McDonald,
Eun deok Mun,
Jordan F. Corbey,
Jamie L. Manson
Abstract:
High field specific heat, Cp, and magnetic susceptibility, \c{hi}, measurements were performed on the quasi-two dimensional Heisenberg antiferromagnet [Cu(pyz)2(pyO)2](PF6)2. While no Cp anomaly is observed down to 0.5 K in zero magnetic field, the application of field parallel to the crystallographic ab-plane induces a lambda-like anomaly in Cp, consistent with Ising-type magnetic order. On the o…
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High field specific heat, Cp, and magnetic susceptibility, \c{hi}, measurements were performed on the quasi-two dimensional Heisenberg antiferromagnet [Cu(pyz)2(pyO)2](PF6)2. While no Cp anomaly is observed down to 0.5 K in zero magnetic field, the application of field parallel to the crystallographic ab-plane induces a lambda-like anomaly in Cp, consistent with Ising-type magnetic order. On the other hand, when the field is parallel to the c-axis, Cp and \c{hi} show evidence of XY-type antiferromagnetism. We argue that it is a small but finite easy-plane anisotropy in quasi-two dimensional [Cu(pyz)2(pyO)2](PF6)2 that allows the unusual observation of field induced XY and Ising-type magnetic states.
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Submitted 14 March, 2011;
originally announced March 2011.
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Magnetic properties of the quasi-two-dimensional S = 1/2 Heisenberg antiferromagnet [Cu(pyz)2(HF2)]PF6
Authors:
E. Cizmar,
S. A. Zvyagin,
R. Beyer,
M. Uhlarz,
M. Ozerov,
Y. Skourski,
J. L. Manson,
J. A. Schlueter,
J. Wosnitza
Abstract:
We report on high-field magnetization, specific-heat and electron spin resonance (ESR) studies of the quasi-two-dimensional spin-1/2 Heisenberg antiferromagnet [Cu(pyz)2(HF2)]PF6. The frequency-field diagram of ESR modes below TN = 4.38 K is described in the frame of the meanfield theory, confirming a collinear magnetic structure with an easy-plane anisotropy. The obtained results allowed us to…
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We report on high-field magnetization, specific-heat and electron spin resonance (ESR) studies of the quasi-two-dimensional spin-1/2 Heisenberg antiferromagnet [Cu(pyz)2(HF2)]PF6. The frequency-field diagram of ESR modes below TN = 4.38 K is described in the frame of the meanfield theory, confirming a collinear magnetic structure with an easy-plane anisotropy. The obtained results allowed us to determine the anisotropy/exchange interaction ratio, A/J = 0.003, and the upper limit for the inter/intra-plane exchange-interaction ratio, J'/J = 1/16. It is argued that despite the onset of 3D long-range magnetic ordering the magnetic properties of this material (including high-magnetic-field magnetization and non-monotonic field dependence of the Neel temperature) are strongly affected by two-dimensional spin correlations.
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Submitted 23 November, 2009;
originally announced November 2009.
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A new collective phenomenon arising from spin anisotropic perturbations to a Heisenberg square lattice manifested in paramagnetic resonance experiments
Authors:
S. Cox,
R. D. McDonald,
J. Singleton,
S. Miller,
P. A. Goddard,
S. El Shawish,
J. Bonca,
J. A. Schlueter,
J. L. Manson
Abstract:
We report unexpected behaviour in a family of Cu spin- 1/2 systems, in which an apparent gap in the low energy magneto-optical absorption spectrum opens at low temperature. This previously unreported collective phenomenon arises at temperatures where the energy of the dominant exchange interaction exceeds the thermal energy. Simulations of the observed shifts in electron paramagnetic resonance s…
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We report unexpected behaviour in a family of Cu spin- 1/2 systems, in which an apparent gap in the low energy magneto-optical absorption spectrum opens at low temperature. This previously unreported collective phenomenon arises at temperatures where the energy of the dominant exchange interaction exceeds the thermal energy. Simulations of the observed shifts in electron paramagnetic resonance spectral weight, which include spin anisotropy, reproduce this behavior yielding the magnitude of the spin anisotropy in these compounds.
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Submitted 3 August, 2009; v1 submitted 20 July, 2009;
originally announced July 2009.
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Isotope effect in quasi-two-dimensional metal-organic antiferromagnets
Authors:
P. A. Goddard,
J. Singleton,
C. Maitland,
S. J. Blundell,
T. Lancaster,
P. J. Baker,
R. D. McDonald,
S. Cox,
P. Sengupta,
J. L. Manson,
K. A. Funk,
J. A. Schlueter
Abstract:
Although the isotope effect in superconducting materials is well-documented, changes in the magnetic properties of antiferromagnets due to isotopic substitution are seldom discussed and remain poorly understood. This is perhaps surprising given the possible link between the quasi-two-dimensional (Q2D) antiferromagnetic and superconducting phases of the layered cuprates. Here we report the experi…
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Although the isotope effect in superconducting materials is well-documented, changes in the magnetic properties of antiferromagnets due to isotopic substitution are seldom discussed and remain poorly understood. This is perhaps surprising given the possible link between the quasi-two-dimensional (Q2D) antiferromagnetic and superconducting phases of the layered cuprates. Here we report the experimental observation of shifts in the Néel temperature and critical magnetic fields ($ΔT_{\rm N}/T_{\rm N}\approx 4%$; $ΔB_{\rm c}/B_{\rm c}\approx 4%$) in a Q2D organic molecular antiferromagnets on substitution of hydrogen for deuterium. These compounds are characterized by strong hydrogen bonds through which the dominant superexchange is mediated. We evaluate how the in-plane and inter-plane exchange energies evolve as the hydrogens on different ligands are substituted, and suggest a possible mechanism for this effect in terms of the relative exchange efficiency of hydrogen and deuterium bonds.
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Submitted 11 July, 2008; v1 submitted 9 July, 2008;
originally announced July 2008.
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Exchange parameters of copper-based quasi-two-dimensional Heisenberg magnets measured using high magnetic fields and muon-spin rotation
Authors:
P. A. Goddard,
J. Singleton,
P. Sengupta,
R. D. McDonald,
T. Lancaster,
S. J. Blundell,
F. L. Pratt,
S. Cox,
N. Harrison,
J. L. Manson,
H. I. Southerland,
J. A. Schlueter
Abstract:
Pulsed-field magnetization experiments (fields $B$ of up to 85 T and temperatures $T$ down to 0.4 K) are reported on nine organic Cu-based two-dimensional (2D) Heisenberg magnets. All compounds show a low-$T$ magnetization that is concave as a function of $B$, with a sharp ``elbow'' transition to a constant value at a field $B_{\rm c}$. Monte-Carlo simulations including a finite interlayer excha…
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Pulsed-field magnetization experiments (fields $B$ of up to 85 T and temperatures $T$ down to 0.4 K) are reported on nine organic Cu-based two-dimensional (2D) Heisenberg magnets. All compounds show a low-$T$ magnetization that is concave as a function of $B$, with a sharp ``elbow'' transition to a constant value at a field $B_{\rm c}$. Monte-Carlo simulations including a finite interlayer exchange energy $J_{\perp}$ quantitatively reproduce the data; the concavity indicates the effective dimensionality and $B_{\rm c}$ is an accurate measure of the in-plane exchange energy $J$. Using these values and Neél temperatures measured by muon-spin rotation, it is also possible to obtain a quantitative estimate of $|J_{\perp}/J|$. In the light of these results, it is suggested that in magnets of the form [Cu(HF$_2$)(pyz)$_2$]X, where X is an anion, the sizes of $J$ and $J_{\perp}$ are controlled by the tilting of the pyrazine (pyz) molecule with respect to the 2D planes.
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Submitted 28 March, 2008;
originally announced March 2008.
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Muon-fluorine entangled states in molecular magnets
Authors:
T. Lancaster,
S. J. Blundell,
P. J. Baker,
M. L. Brooks,
W. Hayes,
F. L. Pratt,
J. L. Manson,
M. M. Conner,
J. A. Schlueter
Abstract:
The information accessible from a muon-spin relaxation experiment is often limited since we lack knowledge of the precise muon stopping site. We demonstrate here the possibility of localizing a spin polarized muon in a known stopping state in a molecular material containing fluorine. The muon-spin precession that results from the entangled nature of the muon-spin and surrounding nuclear spins is…
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The information accessible from a muon-spin relaxation experiment is often limited since we lack knowledge of the precise muon stopping site. We demonstrate here the possibility of localizing a spin polarized muon in a known stopping state in a molecular material containing fluorine. The muon-spin precession that results from the entangled nature of the muon-spin and surrounding nuclear spins is sensitive to the nature of the stopping site and we use this property to identify three classes of site. We are also able to describe the extent to which the muon distorts its surroundings.
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Submitted 18 July, 2007;
originally announced July 2007.
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Magnetic order in the S=1/2 two-dimensional molecular antiferromagnet, copper pyrazine perchlorate Cu(Pz)_2(ClO_4)_2
Authors:
T. Lancaster,
S. J. Blundell,
M. L. Brooks,
P. J. Baker,
F. L. Pratt,
J. L. Manson,
M. M. Conner,
F. Xiao,
C. P. Landee,
F. A. Chaves,
S. Soriano,
M. A. Novak,
T. Papageorgiou,
A. Bianchi,
T. Herrmannsdorfer,
J. Wosnitza,
J. A. Schlueter
Abstract:
We present an investigation of magnetic ordering in the two-dimensional S=1/2 quantum magnet Cu(Pz)_2(ClO_4)_2 using specific heat and zero field muon-spin relaxation (μ^+SR). The magnetic contribution to the specific heat is consistent with an exchange strength of 17.7(3) K. We find unambiguous evidence for a transition to a state of three-dimensional long range order below a critical temperatu…
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We present an investigation of magnetic ordering in the two-dimensional S=1/2 quantum magnet Cu(Pz)_2(ClO_4)_2 using specific heat and zero field muon-spin relaxation (μ^+SR). The magnetic contribution to the specific heat is consistent with an exchange strength of 17.7(3) K. We find unambiguous evidence for a transition to a state of three-dimensional long range order below a critical temperature T_N=4.21(1) K using μ^+SR even though there is no feature in the specific heat at that temperature. The absence of a specific heat anomaly at T_N is consistent with recent theoretical predictions. The ratio of T_N/J=0.24 corresponds to a ratio of intralayer to interlayer exchange constants of |J'/J|=6.8x10^-4, indicative of excellent two-dimensional isolation. The scaled magnetic specific heat of [Cu(Pz)_2(HF_2)]BF_4, a compound with an analogous structure, is essentially identical to that of Cu(Pz)_2(ClO_4)_2 although both differ slightly from the predicted value for an ideal 2D S=1/2 Heisenberg antiferromagnet.
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Submitted 13 December, 2006;
originally announced December 2006.
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Magnetic order in the quasi-one-dimensional spin 1/2 chain, copper pyrazine dinitrate
Authors:
T. Lancaster,
S. J. Blundell,
M. L. Brooks,
P. J. Baker,
F. L. Pratt,
J. L. Manson,
C. P. Landee,
C. Baines
Abstract:
We present the first evidence of magnetic order in the quasi-one-dimensional spin 1/2 molecular chain compound, copper pyrazine dinitrate Cu(C4H4N2)(NO3)2}. Zero field muon-spin relaxation measurements made at dilution refrigerator temperatures show oscillations in the measured asymmetry, characteristic of a quasistatic magnetic field at the muon sites. Our measurements provide convincing eviden…
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We present the first evidence of magnetic order in the quasi-one-dimensional spin 1/2 molecular chain compound, copper pyrazine dinitrate Cu(C4H4N2)(NO3)2}. Zero field muon-spin relaxation measurements made at dilution refrigerator temperatures show oscillations in the measured asymmetry, characteristic of a quasistatic magnetic field at the muon sites. Our measurements provide convincing evidence for long range magnetic order below a temperature T_N=107(1) mK. This leads to an estimate of the interchain coupling constant of |J'|/k_B=0.046 K and to a ratio |J'/J| = 4.4 x 10^-3.
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Submitted 26 October, 2005;
originally announced October 2005.
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Unusual magnetic-field dependence of partially frustrated triangular ordering in manganese tricyanomethanide
Authors:
Ralf Feyerherm,
Anja Loose,
Jamie L. Manson
Abstract:
Manganese tricyanomethanide, Mn[C(CN)3]2, consists of two interpenetrating three-dimensional rutile-like networks. In each network, the tridentate C(CN)3- anion gives rise to superexchange interactions between the Mn2+ ions (S=5/2) that can be mapped onto the "row model" for partially frustrated triangular magnets. We present heat capacity measurements that reveal a phase transition at T_N = 1.1…
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Manganese tricyanomethanide, Mn[C(CN)3]2, consists of two interpenetrating three-dimensional rutile-like networks. In each network, the tridentate C(CN)3- anion gives rise to superexchange interactions between the Mn2+ ions (S=5/2) that can be mapped onto the "row model" for partially frustrated triangular magnets. We present heat capacity measurements that reveal a phase transition at T_N = 1.18K, indicative of magnetic ordering. The zero-field magnetically ordered structure was solved from neutron powder diffraction data taken between 0.04 and 1.2 K. It consists of an incommensurate spiral with a temperature independent propagation vector Q=(2Q 0 0)=(+/-0.622 0 0), where different signs relate to the two different networks. This corresponds to (+/-0.311 +/-0.311 0) in a quasi-hexagonal representation. The ordered moment mu=3.3mu_B is about 2/3 of the full Mn2+ moment. From the values of T_N and Q, the exchange parameters J/k = 0.15 K and J'/J = 0.749 are estimated. The magnetic-field dependence of the intensity of the <2Q 0 0> Bragg reflection, measured for external fields H||Q, indicates the presence of three different magnetic phases. We associate them with the incommensurate spiral (H < 13.5 kOe), an intermediate phase (13.5 kOe < H < 16 kOe), and the "2-1" spin-flop like magnetic structure (H > 16 kOe) proposed for related compounds. For increasing fields, Q continuously approaches the value 1/3, corresponding to the commensurate magnetic structure of the fully frustrated triangular lattice. This value is reached at H_c = 19 kOe. At this point, the field-dependence reverses and Q adopts a value of 0.327 at 26 kOe, the highest field applied in the experiment. Except for H_c, the magnetic ordering is incommensurate in all three magnetic phases of Mn[C(CN)3]2.
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Submitted 8 January, 2003; v1 submitted 26 September, 2002;
originally announced September 2002.