Magnetic ground state and magnetic excitations in black dioptase Cu6Si6O18

Podlesnyak, Andrey A.; Prokhnenko, Oleksandr; Nikitin, Stanislav E.; Kolesnikov, Alexander I.; Matsuda, Masaaki; Dissanayake, Sachith E.; Prisk, T. R.; Nojiri, H.; Díaz-Ortega, I. F.; Kidder, Michelle K.; Anovitz, Lawrence M.

doi:10.1103/PhysRevB.100.184401

Title: Magnetic ground state and magnetic excitations in black dioptase ${Cu}_{6} {Si}_{6} O_{18}$

Abstract

The low-temperature magnetic properties and magnetic structure of fully dehydrated black dioptase ${Cu}_{6} {Si}_{6} O_{18}$ have been studied by single-crystal neutron diffraction and magnetization measurements in magnetic fields up to 30 T. Here, the intrachain $J_{c}$ and interchain $J_{a b}$ interactions as well as the anisotropy of the exchange coupling $J_{c}$ have been determined using inelastic neutron-scattering techniques. Zero-field antiferromagnetic order at $T_{N} = 6.7$ K can be described by a commensurate propagation vector of $k = (0, 0, 3 / 2)$ with respect to the hexagonal $R \bar{3}$ :H unit cell. The Cu magnetic moments are aligned antiferromagnetically along the $c$ axis with about $12^{°}$ tilt and are coupled ferromagnetically between the chains. The high-field magnetization measurements provide strong evidence for the presence of a spin-flop phase above 8 T. We found that $J_{c}$ in black dioptase is significantly increased, while $J_{a b}$ is much weaker compared to its counterpart, green dioptase ${Cu}_{6} [{Si}_{6} O_{18}] 6 H_{2} O$ . We suggest that black dioptase behaves like a nearly ideal $S = 1 / 2$ antiferromagnetic Heisenberg spiral chain with enhanced quantum fluctuations and weak spinon confinement $J_{a b} / J_{c} ~ 0.02$ .

Authors:

^[1]; Prokhnenko, Oleksandr ^[2]; Nikitin, Stanislav E. ^[3];

^[1];

^[1]; Prisk, T. R. ^[4]; Nojiri, H. ^[5]; Díaz-Ortega, I. F. ^[5];

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Helmholtz-Zentrum Berlin für Materialien und Energie, Berlin (Germany)
Max Planck Institute for Chemical Physics of Solids, Dresden (Germany); Technische Univ. Dresden (Germany)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Tohoku Univ., Sendai (Japan)

Publication Date:: Fri Nov 01 00:00:00 EDT 2019

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

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

OSTI Identifier:: 1607105

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Physical Review B

Additional Journal Information:: Journal Volume: 100; Journal Issue: 18; Journal ID: ISSN 2469-9950

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; magnetic interactions; magnetism; 1-dimensional spin chains; antiferromagnets; inelastic neutron scattering; neutron scattering

Citation Formats


                    Podlesnyak, Andrey A., Prokhnenko, Oleksandr, Nikitin, Stanislav E., Kolesnikov, Alexander I., Matsuda, Masaaki, Dissanayake, Sachith E., Prisk, T. R., Nojiri, H., Díaz-Ortega, I. F., Kidder, Michelle K., and Anovitz, Lawrence M. Magnetic ground state and magnetic excitations in black dioptase Cu6Si6O18.  United States: N. p., 2019. 
Web.  doi:10.1103/PhysRevB.100.184401.

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                    Podlesnyak, Andrey A., Prokhnenko, Oleksandr, Nikitin, Stanislav E., Kolesnikov, Alexander I., Matsuda, Masaaki, Dissanayake, Sachith E., Prisk, T. R., Nojiri, H., Díaz-Ortega, I. F., Kidder, Michelle K., & Anovitz, Lawrence M. Magnetic ground state and magnetic excitations in black dioptase Cu6Si6O18.  United States.  https://doi.org/10.1103/PhysRevB.100.184401

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                    Podlesnyak, Andrey A., Prokhnenko, Oleksandr, Nikitin, Stanislav E., Kolesnikov, Alexander I., Matsuda, Masaaki, Dissanayake, Sachith E., Prisk, T. R., Nojiri, H., Díaz-Ortega, I. F., Kidder, Michelle K., and Anovitz, Lawrence M. Fri .  
"Magnetic ground state and magnetic excitations in black dioptase Cu6Si6O18".  United States.  https://doi.org/10.1103/PhysRevB.100.184401.  https://www.osti.gov/servlets/purl/1607105.

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@article{osti_1607105,

  title        = {Magnetic ground state and magnetic excitations in black dioptase Cu6Si6O18},

  author       = {Podlesnyak, Andrey A. and Prokhnenko, Oleksandr and Nikitin, Stanislav E. and Kolesnikov, Alexander I. and Matsuda, Masaaki and Dissanayake, Sachith E. and Prisk, T. R. and Nojiri, H. and Díaz-Ortega, I. F. and Kidder, Michelle K. and Anovitz, Lawrence M.},

  abstractNote = {The low-temperature magnetic properties and magnetic structure of fully dehydrated black dioptase Cu6Si6O18 have been studied by single-crystal neutron diffraction and magnetization measurements in magnetic fields up to 30 T. Here, the intrachain Jc and interchain Jab interactions as well as the anisotropy of the exchange coupling Jc have been determined using inelastic neutron-scattering techniques. Zero-field antiferromagnetic order at TN=6.7 K can be described by a commensurate propagation vector of k=(0,0,3/2) with respect to the hexagonal R3¯:H unit cell. The Cu magnetic moments are aligned antiferromagnetically along the c axis with about 12° tilt and are coupled ferromagnetically between the chains. The high-field magnetization measurements provide strong evidence for the presence of a spin-flop phase above 8 T. We found that Jc in black dioptase is significantly increased, while Jab is much weaker compared to its counterpart, green dioptase Cu6[Si6O18] 6H2O. We suggest that black dioptase behaves like a nearly ideal S=1/2 antiferromagnetic Heisenberg spiral chain with enhanced quantum fluctuations and weak spinon confinement Jab/Jc~0.02.},

  doi          = {10.1103/PhysRevB.100.184401},

  journal      = {Physical Review B},

  number       = 18,

  volume       = 100,

  place        = {United States},

  year         = {Fri Nov 01 00:00:00 EDT 2019},

  month        = {Fri Nov 01 00:00:00 EDT 2019}

}

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Title: Magnetic ground state and magnetic excitations in black dioptase Cu 6 Si 6 O 18

Abstract

Citation Formats

Experiments on ladders reveal a complex interplay between a spin-gapped normal state and superconductivity journal, November 1999

The spin-1/2 Heisenberg chain: thermodynamics, quantum criticality and spin-Peierls exponents journal, October 1998

Quantum magnetism in minerals journal, July 2018

Spin-Wave Spectrum of the Antiferromagnetic Linear Chain journal, December 1962

Spin liquids in frustrated magnets journal, March 2010

Energy Separation of Single-Particle and Continuum States in an S = 1 / 2 Weakly Coupled Chains Antiferromagnet journal, November 2000

Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments journal, November 2014

Stochastic series expansion method with operator-loop update journal, June 1999

Description of Anhydrous (Black) Dioptase as a S = 1/2 Uniform Antiferromagnetic Chain System journal, January 2010

Spinon confinement in a quasi-one-dimensional anisotropic Heisenberg magnet journal, August 2017

Magnetic properties of green dioptase CuSiO3H2O and of black dioptase CuSiO3, and magnetic structure of black dioptase journal, July 1993

Thermodynamic properties of copper silicate: dioptase: Cu6Si6O18·6H2O journal, May 1993

SEQUOIA: A Newly Operating Chopper Spectrometer at the SNS journal, November 2010

Generalized directed loop method for quantum Monte Carlo simulations journal, March 2005

CuSiO 3 : A candidate system for purely oxygen antiferromagnet? journal, July 2003

A comparison of four direct geometry time-of-flight spectrometers at the Spallation Neutron Source journal, April 2014

Structural and chemical varieties of dioptase, Cu 6 [Si 6 O 18 ] · 6H 2 O: II. Structural properties journal, January 1989

The ALPS project release 1.3: Open-source software for strongly correlated systems journal, March 2007

Observation of the spin-Peierls transition in linear Cu 2 + (spin-1/2) chains in an inorganic compound CuGeO 3 journal, June 1993

Recent advances in magnetic structure determination by neutron powder diffraction journal, October 1993

Magnetic susceptibility measurement under high pressure and magnetization measurement of S = 1/2 dioptase lattice antiferromagnet journal, March 2009

Representation analysis of magnetic structures journal, January 1968

Decoupled spin dynamics in the rare-earth orthoferrite YbFeO 3 : Evolution of magnetic excitations through the spin-reorientation transition journal, August 2018

Lead palladium titanate: A room temperature nanoscale multiferroic thin film journal, February 2020

Coupled antiferromagnetic spin- 1 2 chains in green dioptase Cu 6 [ Si 6 O 18 ] · 6 H 2 O journal, February 2016

Crystal structure of copper polysilicate, Cu[SiO3] journal, January 1999

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal, October 2011

Neutron diffraction study of the nuclear and magnetic structure of the quasi-one-dimensional compound CuSiO 3 around T N = 8 K journal, April 2004

Quasi-one-dimensional spin chains in CuSiO3: an EPR study journal, October 2002

Possibility of a spin-Peierls state in CuSiO 3 from electronic structure theory journal, January 2001

The charge-density distribution, its multipole refinement and the antiferromagnetic structure of dioptase, Cu 6 [Si 6 O 18 ]·6H 2 O journal, July 2002

Bose–Einstein condensation in magnetic insulators journal, March 2008

Tomonaga–Luttinger liquid behavior and spinon confinement in YbAlO3 journal, February 2019

Kagome´- and triangular-lattice Heisenberg antiferromagnets: Ordering from quantum fluctuations and quantum-disordered ground states with unconfined bosonic spinons journal, June 1992

Zur Theorie der Metalle: I. Eigenwerte und Eigenfunktionen der linearen Atomkette journal, March 1931

Linear spin wave theory for single-Q incommensurate magnetic structures journal, March 2015

Novel Longitudinal Mode in the Coupled Quantum Chain Compound KCuF 3 journal, July 2000

Excitations in the quantum paramagnetic phase of the quasi-one-dimensional Ising magnet CoNb 2 O 6 in a transverse field: Geometric frustration and quantum renormalization effects journal, July 2014

Large quantum fluctuations in the strongly coupled spin- 1 2 chains of green dioptase Cu 6 Si 6 O 18 ⋅ 6 H 2 O journal, July 2010

Fractional spinon excitations in the quantum Heisenberg antiferromagnetic chain journal, June 2013

CuSiO 3 : A quasi-one-dimensional S = 1 2 antiferromagnetic chain system journal, November 2000

Structural and chemical varieties of dioptase, Cu6[Si6O18] · 6 H2O I. Thermal properties journal, January 1988

The new cold neutron chopper spectrometer at the Spallation Neutron Source: Design and performance journal, August 2011

The cold neutron chopper spectrometer at the Spallation Neutron Source—A review of the first 8 years of operation journal, September 2016

Horace : Software for the analysis of data from single crystal spectroscopy experiments at time-of-flight neutron instruments journal, October 2016

Zur Theorie der Metalle: Erwiderung auf eine Arbeit von A. H. Wilson journal, September 1933

Structural and chemical varieties of dioptase, Cu 6 [Si 6 O 18 ]∙6H 2 O: II. Structural properties journal, August 1989

Structural and chemical varieties of dioptase, Cu 6 [Si 6 O 18 ] · 6 H 2 O*: I. Thermal properties journal, January 1988

Bose-Einstein Condensation in Magnetic Insulators text, January 2007

The ALPS project release 2.0: Open source software for strongly correlated systems text, January 2011

Linear spin wave theory for single-Q incommensurate magnetic structures text, January 2014

Excitations in the quantum paramagnetic phase of the quasi-one-dimensional Ising magnet CoNb$_2$O$_6$ in a transverse field: Geometric frustration and quantum renormalization effects text, January 2014

HORACE: software for the analysis of data from single crystal spectroscopy experiments at time-of-flight neutron instruments text, January 2016

Spinon confinement in a quasi one dimensional anisotropic Heisenberg magnet text, January 2017

Quantum Magnetism in Minerals text, January 2018

Quasi-one-dimensional spin chains in CuSiO3: an EPR study preprint, January 2000

Generalized Directed Loop Method for Quantum Monte Carlo Simulations text, January 2003

Experiments on Ladders Reveal a Complex Interplay between a Spin-Gapped Normal State and Superconductivity text, January 1999

A Novel Longitudinal Mode in the Coupled Quantum Chain Compound KCuF3 text, January 1999

Title: Magnetic ground state and magnetic excitations in black dioptase ${Cu}_{6} {Si}_{6} O_{18}$

Experiments on ladders reveal a complex interplay between a spin-gapped normal state and superconductivity
journal, November 1999

The spin-1/2 Heisenberg chain: thermodynamics, quantum criticality and spin-Peierls exponents
journal, October 1998

Quantum magnetism in minerals
journal, July 2018

Spin-Wave Spectrum of the Antiferromagnetic Linear Chain
journal, December 1962

Spin liquids in frustrated magnets
journal, March 2010

Energy Separation of Single-Particle and Continuum States in an $S = 1 / 2$ Weakly Coupled Chains Antiferromagnet
journal, November 2000

Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments
journal, November 2014

Stochastic series expansion method with operator-loop update
journal, June 1999

Description of Anhydrous (Black) Dioptase as a S = 1/2 Uniform Antiferromagnetic Chain System
journal, January 2010

Spinon confinement in a quasi-one-dimensional anisotropic Heisenberg magnet
journal, August 2017

Magnetic properties of green dioptase CuSiO3H2O and of black dioptase CuSiO3, and magnetic structure of black dioptase
journal, July 1993

Thermodynamic properties of copper silicate: dioptase: Cu6Si6O18·6H2O
journal, May 1993

SEQUOIA: A Newly Operating Chopper Spectrometer at the SNS
journal, November 2010

Generalized directed loop method for quantum Monte Carlo simulations
journal, March 2005

CuSiO ₃ : A candidate system for purely oxygen antiferromagnet?
journal, July 2003

A comparison of four direct geometry time-of-flight spectrometers at the Spallation Neutron Source
journal, April 2014

Structural and chemical varieties of dioptase, Cu ₆ [Si ₆ O ₁₈ ] · 6H ₂ O: II. Structural properties
journal, January 1989

The ALPS project release 1.3: Open-source software for strongly correlated systems
journal, March 2007

Observation of the spin-Peierls transition in linear ${Cu}^{2 +}$ (spin-1/2) chains in an inorganic compound ${CuGeO}_{3}$
journal, June 1993

Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993

Magnetic susceptibility measurement under high pressure and magnetization measurement of S = 1/2 dioptase lattice antiferromagnet
journal, March 2009

Representation analysis of magnetic structures
journal, January 1968

Decoupled spin dynamics in the rare-earth orthoferrite ${YbFeO}_{3}$ : Evolution of magnetic excitations through the spin-reorientation transition
journal, August 2018

Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020

Coupled antiferromagnetic spin- $\frac{1}{2}$ chains in green dioptase ${Cu}_{6} [{Si}_{6} O_{18}] \cdot 6 H_{2} O$
journal, February 2016

Crystal structure of copper polysilicate, Cu[SiO3]
journal, January 1999

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Neutron diffraction study of the nuclear and magnetic structure of the quasi-one-dimensional compound ${CuSiO}_{3}$ around $T_{N} = 8 K$
journal, April 2004

Quasi-one-dimensional spin chains in CuSiO3: an EPR study
journal, October 2002

Possibility of a spin-Peierls state in ${CuSiO}_{3}$ from electronic structure theory
journal, January 2001

The charge-density distribution, its multipole refinement and the antiferromagnetic structure of dioptase, Cu 6 [Si 6 O 18 ]·6H 2 O
journal, July 2002

Bose–Einstein condensation in magnetic insulators
journal, March 2008

Tomonaga–Luttinger liquid behavior and spinon confinement in YbAlO3
journal, February 2019

Kagome´- and triangular-lattice Heisenberg antiferromagnets: Ordering from quantum fluctuations and quantum-disordered ground states with unconfined bosonic spinons
journal, June 1992

Zur Theorie der Metalle: I. Eigenwerte und Eigenfunktionen der linearen Atomkette
journal, March 1931

Linear spin wave theory for single-Q incommensurate magnetic structures
journal, March 2015

Novel Longitudinal Mode in the Coupled Quantum Chain Compound ${KCuF}_{3}$
journal, July 2000

Excitations in the quantum paramagnetic phase of the quasi-one-dimensional Ising magnet ${CoNb}_{2}$ $O_{6}$ in a transverse field: Geometric frustration and quantum renormalization effects
journal, July 2014

Large quantum fluctuations in the strongly coupled spin- $\frac{1}{2}$ chains of green dioptase ${Cu}_{6} {Si}_{6} O_{18} \cdot 6 H_{2} O$
journal, July 2010

Fractional spinon excitations in the quantum Heisenberg antiferromagnetic chain
journal, June 2013

${CuSiO}_{3} :$ A quasi-one-dimensional $S = \frac{1}{2}$ antiferromagnetic chain system
journal, November 2000

Structural and chemical varieties of dioptase, Cu6[Si6O18] · 6 H2O I. Thermal properties
journal, January 1988

The new cold neutron chopper spectrometer at the Spallation Neutron Source: Design and performance
journal, August 2011

The cold neutron chopper spectrometer at the Spallation Neutron Source—A review of the first 8 years of operation
journal, September 2016

Horace : Software for the analysis of data from single crystal spectroscopy experiments at time-of-flight neutron instruments
journal, October 2016

Zur Theorie der Metalle: Erwiderung auf eine Arbeit von A. H. Wilson
journal, September 1933

Structural and chemical varieties of dioptase, Cu ₆ [Si ₆ O ₁₈ ]∙6H ₂ O: II. Structural properties
journal, August 1989

Structural and chemical varieties of dioptase, Cu ₆ [Si ₆ O ₁₈ ] · 6 H ₂ O*: I. Thermal properties
journal, January 1988

Bose-Einstein Condensation in Magnetic Insulators
text, January 2007

The ALPS project release 2.0: Open source software for strongly correlated systems
text, January 2011

Linear spin wave theory for single-Q incommensurate magnetic structures
text, January 2014

Excitations in the quantum paramagnetic phase of the quasi-one-dimensional Ising magnet CoNb$_2$O$_6$ in a transverse field: Geometric frustration and quantum renormalization effects
text, January 2014

HORACE: software for the analysis of data from single crystal spectroscopy experiments at time-of-flight neutron instruments
text, January 2016

Spinon confinement in a quasi one dimensional anisotropic Heisenberg magnet
text, January 2017

Quantum Magnetism in Minerals
text, January 2018

Quasi-one-dimensional spin chains in CuSiO3: an EPR study
preprint, January 2000

Generalized Directed Loop Method for Quantum Monte Carlo Simulations
text, January 2003

Experiments on Ladders Reveal a Complex Interplay between a Spin-Gapped Normal State and Superconductivity
text, January 1999

A Novel Longitudinal Mode in the Coupled Quantum Chain Compound KCuF3
text, January 1999