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Title: Moment-Volume Coupling in La(Fe1-xSix)13

Abstract

We investigate the origin of the volume change and magnetoelastic interaction observed at the magnetic first-order transition in the magnetocaloric system La(Fe1-xSix)13 by means of first-principles calculations combined with the fixed-spin moment approach. Here, we find that the volume of the system varies with the square of the average local Fe moment, which is significantly smaller in the spin disordered configurations compared to the ferromagnetic ground state. The vibrational density of states obtained for a hypothetical ferromagnetic state with artificially reduced spin-moments compared to a nuclear inelastic X-ray scattering measurement directly above the phase transition reveals that the anomalous softening at the transition essentially depends on the same moment-volume coupling mechanism. Finally, in the same spirit, the dependence of the average local Fe moment on the Si content can account for the occurence of first- and second-order transitions in the system.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [3];  [3];  [3];  [3];  [4];  [1]
  1. Univ. of Duisburg-Essen,Duisburg (Germany). Faculty of Physics and Center for Nanointegration (CENIDE)
  2. Leibniz Inst. for Solid State and Materials Research (IFW), Dresden (Germany)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  4. Technische Univ. Darmstadt (Germany). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
German Research Foundation (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465142
Alternate Identifier(s):
OSTI ID: 1413836
Grant/Contract Number:  
AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physica Status Solidi B. Basic Solid State Physics
Additional Journal Information:
Journal Volume: 255; Journal Issue: 2; Journal ID: ISSN 0370-1972
Publisher:
Wiley-Blackwell
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Invar effect; La-Fe-Si compounds; density functional theory; magnetocaloric effect; magnetoelastic coupling; nuclear resonanant inelastic x-ray scattering

Citation Formats

Gruner, Markus E., Keune, Werner, Landers, Joachim, Salamon, Soma, Krautz, Maria, Zhao, Jiyong, Hu, Michael Y., Toellner, Thomas, Alp, Esen E., Gutfleisch, Oliver, and Wende, Heiko. Moment-Volume Coupling in La(Fe1-xSix)13. United States: N. p., 2017. Web. doi:10.1002/pssb.201700465.
Gruner, Markus E., Keune, Werner, Landers, Joachim, Salamon, Soma, Krautz, Maria, Zhao, Jiyong, Hu, Michael Y., Toellner, Thomas, Alp, Esen E., Gutfleisch, Oliver, & Wende, Heiko. Moment-Volume Coupling in La(Fe1-xSix)13. United States. doi:10.1002/pssb.201700465.
Gruner, Markus E., Keune, Werner, Landers, Joachim, Salamon, Soma, Krautz, Maria, Zhao, Jiyong, Hu, Michael Y., Toellner, Thomas, Alp, Esen E., Gutfleisch, Oliver, and Wende, Heiko. Mon . "Moment-Volume Coupling in La(Fe1-xSix)13". United States. doi:10.1002/pssb.201700465. https://www.osti.gov/servlets/purl/1465142.
@article{osti_1465142,
title = {Moment-Volume Coupling in La(Fe1-xSix)13},
author = {Gruner, Markus E. and Keune, Werner and Landers, Joachim and Salamon, Soma and Krautz, Maria and Zhao, Jiyong and Hu, Michael Y. and Toellner, Thomas and Alp, Esen E. and Gutfleisch, Oliver and Wende, Heiko},
abstractNote = {We investigate the origin of the volume change and magnetoelastic interaction observed at the magnetic first-order transition in the magnetocaloric system La(Fe1-xSix)13 by means of first-principles calculations combined with the fixed-spin moment approach. Here, we find that the volume of the system varies with the square of the average local Fe moment, which is significantly smaller in the spin disordered configurations compared to the ferromagnetic ground state. The vibrational density of states obtained for a hypothetical ferromagnetic state with artificially reduced spin-moments compared to a nuclear inelastic X-ray scattering measurement directly above the phase transition reveals that the anomalous softening at the transition essentially depends on the same moment-volume coupling mechanism. Finally, in the same spirit, the dependence of the average local Fe moment on the Si content can account for the occurence of first- and second-order transitions in the system.},
doi = {10.1002/pssb.201700465},
journal = {Physica Status Solidi B. Basic Solid State Physics},
number = 2,
volume = 255,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Lattice structure of cubic LaFe11.5Si1.5 with space group 226 (Fm$\bar{3}$c). La (purple spheres) resides on the 8a Wyckoff position, FeI (bright blue) on 8b, while FeII (dark blue) and Si (yellow) share the 96i sites. In the calculation, a pseudodisordered configuration was used, where Si resides on specificmore » 96i site such that rhombohedral symmetry (space group 146) is retained. Top panel: Unit cell with 112 atoms and Cartesian basis as used in the calculations. Bottom: Primitive cell with two formula units (28 atoms) and fcc basis vectors.« less

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Works referenced in this record:

Novel Design of La(Fe,Si)13 Alloys Towards High Magnetic Refrigeration Performance
journal, August 2010

  • Lyubina, Julia; Schäfer, Rudolf; Martin, Norbert
  • Advanced Materials, Vol. 22, Issue 33
  • DOI: 10.1002/adma.201000177

Impact of local lattice distortions on the structural stability of Fe-Pd magnetic shape-memory alloys
journal, June 2011


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Phonon softening and metallization of a narrow-gap semiconductor by thermal disorder
journal, March 2011

  • Delaire, O.; Marty, K.; Stone, M. B.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 12
  • DOI: 10.1073/pnas.1014869108

Efficient Room-Temperature Cooling with Magnets
journal, June 2016


Giant magnetocaloric effect driven by structural transitions
journal, May 2012

  • Liu, Jian; Gottschall, Tino; Skokov, Konstantin P.
  • Nature Materials, Vol. 11, Issue 7
  • DOI: 10.1038/nmat3334

Magnetic and electronic studies of LaFe13−xSix compounds with 1.3≤x≤1.69
journal, December 2013


Effect of temperature and compositional changes on the phonon properties of Ni-Mn-Ga shape memory alloys
journal, October 2012


Binding mechanism and itinerant magnetism of ZrFe2 and YFe2
journal, May 1985


Ferromagnetic phases of bcc and fcc Fe, Co, and Ni
journal, August 1986


Large magnetocaloric effect in La(FexSi1−x)13 itinerant-electron metamagnetic compounds
journal, August 2002

  • Fujieda, S.; Fujita, A.; Fukamichi, K.
  • Applied Physics Letters, Vol. 81, Issue 7
  • DOI: 10.1063/1.1498148

Stability and Magnetocaloric Properties of Sintered La(Fe, Mn, Si)$_{13}$H$_{z}$ Alloys
journal, October 2011


Noncollinear magnetic structures in amorphous iron and iron-based alloys
journal, January 1995


Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Origin of the Invar effect in iron–nickel alloys
journal, July 1999

  • van Schilfgaarde, Mark; Abrikosov, I. A.; Johansson, B.
  • Nature, Vol. 400, Issue 6739
  • DOI: 10.1038/21848

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Magnetic properties of iron-rich Fe-Zr glasses
journal, June 1987


Energy Dependence of Nuclear Recoil Measured with Incoherent Nuclear Scattering of Synchrotron Radiation
journal, June 1995


Exploring La(Fe,Si)13-based magnetic refrigerants towards application
journal, September 2012


Phonon Density of States Measured by Inelastic Nuclear Resonant Scattering
journal, May 1995


PHON: A program to calculate phonons using the small displacement method
journal, December 2009


Mixed Magnetism for Refrigeration and Energy Conversion
journal, September 2011

  • Dung, Nguyen H.; Ou, Zhi Qiang; Caron, Luana
  • Advanced Energy Materials, Vol. 1, Issue 6
  • DOI: 10.1002/aenm.201100252

Giant volume magnetostriction due to the itinerant electron metamagnetic transition in La(Fe-Si)/sub 13/ compounds
journal, January 1999

  • Fujita, A.; Fukamichi, K.
  • IEEE Transactions on Magnetics, Vol. 35, Issue 5
  • DOI: 10.1109/20.800668

Inverse barocaloric effect in the giant magnetocaloric La–Fe–Si–Co compound
journal, September 2011

  • Mañosa, Lluís; González-Alonso, David; Planes, Antoni
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1606

Ab initio Prediction of Martensitic and Intermartensitic Phase Boundaries in Ni-Mn-Ga
journal, January 2016


High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Entropy changes associated with the first-order magnetic transition in LaFe13−xSix
journal, December 2006

  • Jia, L.; Liu, G. J.; Sun, J. R.
  • Journal of Applied Physics, Vol. 100, Issue 12
  • DOI: 10.1063/1.2404468

Caloric Effects in Ferroic Materials: New Concepts for Cooling
journal, November 2011

  • Fähler, Sebastian; Rößler, Ulrich K.; Kastner, Oliver
  • Advanced Engineering Materials, Vol. 14, Issue 1-2
  • DOI: 10.1002/adem.201100178

Large magnetic entropy change and magnetic properties in La (Fe 1- x Mn x ) 11.7 Si 1.3 H y compounds
journal, July 2003


Mössbauer spectroscopic evaluation of chemical and electronic distributions in La(Fe0.81Si0.19)13
journal, March 2004

  • Hamdeh, H. H.; Al-Ghanem, H.; Hikal, W. M.
  • Journal of Magnetism and Magnetic Materials, Vol. 269, Issue 3
  • DOI: 10.1016/j.jmmm.2003.07.004

Low-temperature specific heat in hydrogenated and Mn-doped La ( Fe , Si ) 13
journal, October 2016


Entropy change at magnetic phase transitions of the first order and second order
journal, January 2014


Recent developments in magnetocaloric materials
journal, May 2005

  • Gschneidner, K. A.; Pecharsky, V. K.; Tsokol, A. O.
  • Reports on Progress in Physics, Vol. 68, Issue 6, p. 1479-1539
  • DOI: 10.1088/0034-4885/68/6/R04

High-spin and low-spin states in Invar and related alloys
journal, April 1990


Magnetic refrigeration: phase transitions, itinerant magnetism and spin fluctuations
journal, January 2012


First-Principles Determination of the Soft Mode in Cubic ZrO 2
journal, May 1997


Magnetic coupling in transition-metal–doped LaSiFe 11.5 TM 0.5 (TM=Cr, Mn, Co and Ni)
journal, May 2015


Mössbauer effect probe of field-induced magnetic phase transitionin LaFe13−xSix intermetallic compounds
journal, September 2004

  • Cheng, Zhao-hua; Di, Nai-li; Li, Qing-an
  • Applied Physics Letters, Vol. 85, Issue 10
  • DOI: 10.1063/1.1789235

Generalized gradient approximation for the exchange-correlation hole of a many-electron system
journal, December 1996


Caloric materials near ferroic phase transitions
journal, April 2014

  • Moya, X.; Kar-Narayan, S.; Mathur, N. D.
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3951

Amorphous yttrium-iron alloys. II. Mossbauer spectra
journal, December 1981


Magnetocaloric materials: The search for new systems
journal, September 2012


Observation of Nuclear Resonant Scattering Accompanied by Phonon Excitation Using Synchrotron Radiation
journal, May 1995


Amorphous yttrium-iron alloys. I. Magnetic properties
journal, December 1981


Positive Vibrational Entropy of Chemical Ordering in FeV
journal, September 2011


Small‐angle neutron scattering evidence for the absence of long‐range magnetic order in amorphous Fe 9 1 Zr 9
journal, April 1985

  • Rhyne, J. J.; Fish, G. E.
  • Journal of Applied Physics, Vol. 57, Issue 8
  • DOI: 10.1063/1.335110

Local electronic and magnetic properties of pure and Mn-containing magnetocaloric LaFe 13− x Si x compounds inferred from Mössbauer spectroscopy and magnetometry
journal, July 2015


Local magnetic properties of iron-rich amorphous Fe100−xZrx alloys
journal, January 1990


First-principles calculations of the instability leading to the Invar effect
journal, April 1993


Thermal expansion coefficients of LaFe 11.7 Si 1.3
journal, December 2002

  • Chang, Hong; Liang, Jing-Kui; Shen, Bao-Gen
  • Journal of Physics D: Applied Physics, Vol. 36, Issue 2
  • DOI: 10.1088/0022-3727/36/2/314

Understanding the Phase Transitions of the Ni 2 MnGa Magnetic Shape Memory System from First Principles
journal, January 2009


Transverse spin freezing in a ‐Fe 9 2 Zr 8 (invited)
journal, November 1988

  • Ryan, D. H.; Strom‐Olsen, J. O.; Provencher, R.
  • Journal of Applied Physics, Vol. 64, Issue 10
  • DOI: 10.1063/1.342206

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Analytical model to understand the colossal magnetocaloric effect
journal, February 2005


Neutron diffraction study of LaFe11.31Si1.69 and LaFe11.31Si1.69H1.45 compounds
journal, February 2010


Itinerant-electron metamagnetic transition and large magnetovolume effects in La ( Fe x Si 1 x ) 13 compounds
journal, November 2001


Ab initio full-potential study of the structural and magnetic phase stability of iron
journal, August 1999


Inhomogeneous Electron Gas
journal, November 1964


Large magnetovolume effects and band structure of itinerant-electron metamagnetic La ( Fe x Si 1 x ) 13 compounds
journal, September 2003


Giant solid-state barocaloric effect in the Ni–Mn–In magnetic shape-memory alloy
journal, April 2010

  • Mañosa, Lluís; González-Alonso, David; Planes, Antoni
  • Nature Materials, Vol. 9, Issue 6
  • DOI: 10.1038/nmat2731

Giant Magnetocaloric Effect in Gd5(Si2Ge2)
journal, June 1997


Mechanism of the strong magnetic refrigerant performance of LaFe 13 x Si x
journal, September 2007


Modeling specific heat and entropy change in La(Fe–Mn–Si)13–H compounds
journal, February 2016

  • Piazzi, Marco; Bennati, Cecilia; Curcio, Carmen
  • Journal of Magnetism and Magnetic Materials, Vol. 400
  • DOI: 10.1016/j.jmmm.2015.07.055

Covalent magnetism: An alternative to the Stoner model
journal, March 1981

  • Williams, A. R.; Zeller, R.; Moruzzi, V. L.
  • Journal of Applied Physics, Vol. 52, Issue 3
  • DOI: 10.1063/1.329617

Alloys of the FeRh system as a new class of working material for magnetic refrigerators
journal, January 1992


Systematic study of the microstructure, entropy change and adiabatic temperature change in optimized La–Fe–Si alloys
journal, May 2011


Mastering hysteresis in magnetocaloric materials
journal, August 2016

  • Gutfleisch, O.; Gottschall, T.; Fries, M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2074
  • DOI: 10.1098/rsta.2015.0308

Dynamics of the First-Order Metamagnetic Transition in Magnetocaloric La(Fe,Si) 13 : Reducing Hysteresis
journal, November 2014

  • Lovell, Edmund; Pereira, André M.; Caplin, A. David
  • Advanced Energy Materials, Vol. 5, Issue 6
  • DOI: 10.1002/aenm.201401639

Study of the critical behaviour of the magnetization and electrical resistivity in cubic La(Fe, Si)13 compounds
journal, April 1983

  • Palstra, T. T. M.; Mydosh, J. A.; Nieuwenhuys, G. J.
  • Journal of Magnetism and Magnetic Materials, Vol. 36, Issue 3
  • DOI: 10.1016/0304-8853(83)90128-2

Systematic investigation of Mn substituted La(Fe,Si)13 alloys and their hydrides for room-temperature magnetocaloric application
journal, June 2014


Magnetic Materials and Devices for the 21st Century: Stronger, Lighter, and More Energy Efficient
journal, December 2010

  • Gutfleisch, Oliver; Willard, Matthew A.; Brück, Ekkes
  • Advanced Materials, Vol. 23, Issue 7
  • DOI: 10.1002/adma.201002180

Ab initio Force Constant Approach to Phonon Dispersion Relations of Diamond and Graphite
journal, December 1995


Magnetocaloric effect and the influence of pressure on magnetic properties of La-excess pseudo-binary alloys La 1+δ (Fe 0.85 Si 0.15 ) 13
journal, October 2016

  • Vuong, Van Hiep; Do Thi, Kim Anh; Thuan Nguyen, Khac
  • Journal of Applied Physics, Vol. 120, Issue 14
  • DOI: 10.1063/1.4961715

Structural and magnetic properties of magnetocaloric LaFe13–xSix compounds synthesized by high energy ball-milling
journal, December 2010


Element-Resolved Thermodynamics of Magnetocaloric LaFe 13 x Si x
journal, February 2015


Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994


Hyperfine interactions and band structures of LaFe13−xSix intermetallic compounds with large magnetic entropy changes
journal, August 2006

  • Wang, Guang-jun; Wang, Fang; Di, Nai-li
  • Journal of Magnetism and Magnetic Materials, Vol. 303, Issue 1
  • DOI: 10.1016/j.jmmm.2005.10.231

Explanation of the Invar Anomalies from Molecular-Orbital Cluster Calculations
journal, July 1981


Adiabatic Electron-Phonon Interaction and High-Temperature Thermodynamics of A 15 Compounds
journal, September 2008


Phase equilibria in the Fe–La–Si ternary system
journal, January 2012


Transition Metal Based Magneto Caloric Materials for Energy Efficient Heat Pumps
journal, October 2016


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.