skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Abstract

Spin–phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here in this paper, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1–2 cm-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. In conclusion, this work spectroscopically reveals and quantitates the spin–phonon couplings in typical transition metal complexes and sheds light on the origin of the spin–phonon entanglement.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [4];  [3];  [3]; ORCiD logo [3]; ORCiD logo [5];  [4]; ORCiD logo [4];  [1]; ORCiD logo [6]; ORCiD logo [7];  [8]; ORCiD logo [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Florida A&M Univ., Tallahassee, FL (United States). Dept. of Physics
  3. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS), Chemical and Engineering Materials Division
  5. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  6. Max Planck Inst. for Coal Research, Mülheim, (Germany); Bulgarian Academy of Sciences, Sofia (Bulgaria). Inst. of General and Inorganic Chemistry
  7. Max Planck Inst. for Chemical Energy Conversion, Mülheim (Germany)
  8. Max Planck Inst. for Coal Research, Mülheim, (Germany)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1468922
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Moseley, Duncan H., Stavretis, Shelby E., Thirunavukkuarasu, Komalavalli, Ozerov, Mykhaylo, Cheng, Yongqiang, Daemen, Luke L., Ludwig, Jonathan, Lu, Zhengguang, Smirnov, Dmitry, Brown, Craig M., Pandey, Anup, Ramirez-Cuesta, A. J., Lamb, Adam C., Atanasov, Mihail, Bill, Eckhard, Neese, Frank, and Xue, Zi-Ling. Spin–phonon couplings in transition metal complexes with slow magnetic relaxation. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04896-0.
Moseley, Duncan H., Stavretis, Shelby E., Thirunavukkuarasu, Komalavalli, Ozerov, Mykhaylo, Cheng, Yongqiang, Daemen, Luke L., Ludwig, Jonathan, Lu, Zhengguang, Smirnov, Dmitry, Brown, Craig M., Pandey, Anup, Ramirez-Cuesta, A. J., Lamb, Adam C., Atanasov, Mihail, Bill, Eckhard, Neese, Frank, & Xue, Zi-Ling. Spin–phonon couplings in transition metal complexes with slow magnetic relaxation. United States. doi:10.1038/s41467-018-04896-0.
Moseley, Duncan H., Stavretis, Shelby E., Thirunavukkuarasu, Komalavalli, Ozerov, Mykhaylo, Cheng, Yongqiang, Daemen, Luke L., Ludwig, Jonathan, Lu, Zhengguang, Smirnov, Dmitry, Brown, Craig M., Pandey, Anup, Ramirez-Cuesta, A. J., Lamb, Adam C., Atanasov, Mihail, Bill, Eckhard, Neese, Frank, and Xue, Zi-Ling. Tue . "Spin–phonon couplings in transition metal complexes with slow magnetic relaxation". United States. doi:10.1038/s41467-018-04896-0. https://www.osti.gov/servlets/purl/1468922.
@article{osti_1468922,
title = {Spin–phonon couplings in transition metal complexes with slow magnetic relaxation},
author = {Moseley, Duncan H. and Stavretis, Shelby E. and Thirunavukkuarasu, Komalavalli and Ozerov, Mykhaylo and Cheng, Yongqiang and Daemen, Luke L. and Ludwig, Jonathan and Lu, Zhengguang and Smirnov, Dmitry and Brown, Craig M. and Pandey, Anup and Ramirez-Cuesta, A. J. and Lamb, Adam C. and Atanasov, Mihail and Bill, Eckhard and Neese, Frank and Xue, Zi-Ling},
abstractNote = {Spin–phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here in this paper, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1–2 cm-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. In conclusion, this work spectroscopically reveals and quantitates the spin–phonon couplings in typical transition metal complexes and sheds light on the origin of the spin–phonon entanglement.},
doi = {10.1038/s41467-018-04896-0},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

Far infrared magnetic resonance in FeSiF 6 ⋅6H 2 O and Fe(SPh) 4 2−
journal, March 1977

  • Champion, P. M.; Sievers, A. J.
  • The Journal of Chemical Physics, Vol. 66, Issue 5
  • DOI: 10.1063/1.434200

Geometry-Mediated Enhancement of Single-Ion Anisotropy: A Route to Single-Molecule Magnets with a High Blocking Temperature
journal, October 2013

  • Dey, Mamon; Gogoi, Nayanmoni
  • Angewandte Chemie International Edition, Vol. 52, Issue 49
  • DOI: 10.1002/anie.201304982

The Electronic Ground State of [V(urea) 6 ] 3+ Probed by NIR Luminescence, Electronic Raman, and High-Field EPR Spectroscopies
journal, April 2006

  • Beaulac, Rémi; Tregenna-Piggott, Philip L. W.; Barra, Anne-Laure
  • Inorganic Chemistry, Vol. 45, Issue 8
  • DOI: 10.1021/ic051709f

Electron-Phonon and Magnetoelastic Interactions in Ferromagnetic Co [ N ( CN ) 2 ] 2
journal, July 2013


Projector augmented-wave method
journal, December 1994


The rise of 3-d single-ion magnets in molecular magnetism: towards materials from molecules?
journal, January 2016

  • Frost, Jamie M.; Harriman, Katie L. M.; Murugesu, Muralee
  • Chemical Science, Vol. 7, Issue 4
  • DOI: 10.1039/C5SC03224E

Electronic Raman transitions from the vanadium(III) hexa-aqua cation, in guanidinium vanadium sulphate
journal, April 2001


Measuring giant anisotropy in paramagnetic transition metal complexes with relevance to single-ion magnetism
journal, January 2016

  • Krzystek, J.; Telser, Joshua
  • Dalton Transactions, Vol. 45, Issue 42
  • DOI: 10.1039/C6DT01754A

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


Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni II Se 4 Coordination Complex
journal, September 2015

  • Jiang, Shang-Da; Maganas, Dimitrios; Levesanos, Nikolaos
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b06716

What is not required to make a single molecule magnet
journal, January 2011

  • Neese, Frank; Pantazis, Dimitrios A.
  • Faraday Discuss., Vol. 148
  • DOI: 10.1039/C005256F

Molecular magnetic hysteresis at 60 kelvin in dysprosocenium
journal, August 2017

  • Goodwin, Conrad A. P.; Ortu, Fabrizio; Reta, Daniel
  • Nature, Vol. 548, Issue 7668
  • DOI: 10.1038/nature23447

First-principles prediction of redox potentials in transition-metal compounds with LDA + U
journal, December 2004


Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

Frequency domain Fourier transform THz-EPR on single molecule magnets using coherent synchrotron radiation
journal, January 2009

  • Schnegg, Alexander; Behrends, Jan; Lips, Klaus
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 31
  • DOI: 10.1039/b905745e

Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings
journal, October 2015


Zero-field splitting in metal complexes
journal, May 2004


Radical ligand-containing single-molecule magnets
journal, April 2015


Far-infrared studies on hemin and hemin-like complexes
journal, March 1971


Electronic structure and magnetic properties of high-spin octahedral Co(II) complexes: Co(II)(acac)2(H2O)2
journal, December 1999

  • Lohr, Lawrence L.; Miller, Jeremy C.; Sharp, Robert R.
  • The Journal of Chemical Physics, Vol. 111, Issue 22
  • DOI: 10.1063/1.480365

Intra-molecular origin of the spin-phonon coupling in slow-relaxing molecular magnets
journal, January 2017

  • Lunghi, Alessandro; Totti, Federico; Sanvito, Stefano
  • Chemical Science, Vol. 8, Issue 9
  • DOI: 10.1039/C7SC02832F

Far‐Infrared Magnetic Resonance in Fe(III) and Mn(III) Porphyrins, Myoglobin, Hemoglobin, Ferrichrome A, and Fe(III) Dithiocarbamates
journal, May 1971

  • Brackett, G. C.; Richards, P. L.; Caughey, W. S.
  • The Journal of Chemical Physics, Vol. 54, Issue 10
  • DOI: 10.1063/1.1674688

Variable temperature inelastic neutron scattering study of chromium(II) Tutton salt: manifestation of the 5E⊗e Jahn–Teller effect
journal, August 2002

  • Dobe, Christopher; Andres, Hans-Peter; Tregenna-Piggott, Philip L. W.
  • Chemical Physics Letters, Vol. 362, Issue 5-6
  • DOI: 10.1016/S0009-2614(02)01131-4

Exploiting single-ion anisotropy in the design of f-element single-molecule magnets
journal, January 2011

  • Rinehart, Jeffrey D.; Long, Jeffrey R.
  • Chemical Science, Vol. 2, Issue 11
  • DOI: 10.1039/c1sc00513h

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect
journal, March 2005

  • Carver, Graham; Spichiger, David; Tregenna-Piggott, Philip L. W.
  • The Journal of Chemical Physics, Vol. 122, Issue 12
  • DOI: 10.1063/1.1872835

3d single-ion magnets
journal, January 2015

  • Craig, Gavin A.; Murrie, Mark
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00439F

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


First principles phonon calculations in materials science
journal, November 2015


Comprehensive Spectroscopic Determination of the Crystal Field Splitting in an Erbium Single-Ion Magnet
journal, September 2015

  • Rechkemmer, Yvonne; Fischer, Julia E.; Marx, Raphael
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08344

Lanthanide single molecule magnets: progress and perspective
journal, January 2015

  • Zhang, Peng; Zhang, Li; Tang, Jinkui
  • Dalton Transactions, Vol. 44, Issue 9
  • DOI: 10.1039/C4DT03329A

ESR spectra of low-symmetry high-spin cobalt(II) complexes. 6. 6-Methylquinoline, pyridine, and water adducts of cobalt(II) acetylacetonate
journal, October 1980

  • Bencini, A.; Benelli, C.; Gatteschi, D.
  • Inorganic Chemistry, Vol. 19, Issue 10
  • DOI: 10.1021/ic50212a037

Determining Key Local Vibrations in the Relaxation of Molecular Spin Qubits and Single-Molecule Magnets
journal, March 2017

  • Escalera-Moreno, L.; Suaud, N.; Gaita-Ariño, A.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
  • DOI: 10.1021/acs.jpclett.7b00479

A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier
journal, February 2016

  • Rechkemmer, Yvonne; Breitgoff, Frauke D.; van der Meer, Margarethe
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10467

Quantum Tunneling of Magnetization and Related Phenomena in Molecular Materials
journal, January 2003

  • Gatteschi, Dante; Sessoli, Roberta
  • Angewandte Chemie International Edition, Vol. 42, Issue 3
  • DOI: 10.1002/anie.200390099

An easy way to perdeuterated pyrazoles by catalytic exchange reactions
journal, July 2001


Organometallic Single-Molecule Magnets
journal, January 2014


Origin of slow magnetic relaxation in Kramers ions with non-uniaxial anisotropy
journal, July 2014

  • Gómez-Coca, Silvia; Urtizberea, Ainhoa; Cremades, Eduard
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5300

Far infrared spectra of magnetic ions in crystals
journal, September 1972


Structure and Bonding of the Vanadium(III) Hexa-Aqua Cation. 2. Manifestation of Dynamical Jahn−Teller Coupling in Axially Distorted Vanadium(III) Complexes
journal, December 2004

  • Tregenna-Piggott, Philip L. W.; Carver, Graham
  • Inorganic Chemistry, Vol. 43, Issue 25
  • DOI: 10.1021/ic049291t

    Works referencing / citing this record:

    CCDC 1842460: Experimental Crystal Structure Determination: CODAAC06 : bis(deuterium oxide)-bis(perdeuteroacetylacetonato)-cobalt
    dataset, May 2018

    • Moseley, Duncan H.; Stavretis, Shelby E.; Thirunavukkuarasu, Komalavalli
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1zv768

    CCDC 1842364: Experimental Crystal Structure Determination: CODAAC05 : bis(acetylacetonato)-diaqua-cobalt
    dataset, May 2018

    • Moseley, Duncan H.; Stavretis, Shelby E.; Thirunavukkuarasu, Komalavalli
    • Cambridge Structural Database (CSD)
    • DOI: 10.5517/ccdc.csd.cc1zv432

    Quantum Tunneling of Magnetization and Related Phenomena in Molecular Materials
    journal, January 2003

    • Gatteschi, Dante; Sessoli, Roberta
    • Angewandte Chemie International Edition, Vol. 42, Issue 3
    • DOI: 10.1002/anie.200390099

    Geometry-Mediated Enhancement of Single-Ion Anisotropy: A Route to Single-Molecule Magnets with a High Blocking Temperature
    journal, October 2013

    • Dey, Mamon; Gogoi, Nayanmoni
    • Angewandte Chemie International Edition, Vol. 52, Issue 49
    • DOI: 10.1002/anie.201304982

    Far-infrared studies on hemin and hemin-like complexes
    journal, March 1971


    Zero-field splitting in metal complexes
    journal, May 2004


    Radical ligand-containing single-molecule magnets
    journal, April 2015


    First principles phonon calculations in materials science
    journal, November 2015


    Magnetic Transitions in Iron Porphyrin Halides by Inelastic Neutron Scattering and Ab Initio Studies of Zero-Field Splittings
    journal, October 2015


    Determining Key Local Vibrations in the Relaxation of Molecular Spin Qubits and Single-Molecule Magnets
    journal, March 2017

    • Escalera-Moreno, L.; Suaud, N.; Gaita-Ariño, A.
    • The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
    • DOI: 10.1021/acs.jpclett.7b00479

    Structure and Bonding of the Vanadium(III) Hexa-Aqua Cation. 2. Manifestation of Dynamical Jahn−Teller Coupling in Axially Distorted Vanadium(III) Complexes
    journal, December 2004

    • Tregenna-Piggott, Philip L. W.; Carver, Graham
    • Inorganic Chemistry, Vol. 43, Issue 25
    • DOI: 10.1021/ic049291t

    The Electronic Ground State of [V(urea) 6 ] 3+ Probed by NIR Luminescence, Electronic Raman, and High-Field EPR Spectroscopies
    journal, April 2006

    • Beaulac, Rémi; Tregenna-Piggott, Philip L. W.; Barra, Anne-Laure
    • Inorganic Chemistry, Vol. 45, Issue 8
    • DOI: 10.1021/ic051709f

    ESR spectra of low-symmetry high-spin cobalt(II) complexes. 6. 6-Methylquinoline, pyridine, and water adducts of cobalt(II) acetylacetonate
    journal, October 1980

    • Bencini, A.; Benelli, C.; Gatteschi, D.
    • Inorganic Chemistry, Vol. 19, Issue 10
    • DOI: 10.1021/ic50212a037

    Direct Observation of Very Large Zero-Field Splitting in a Tetrahedral Ni II Se 4 Coordination Complex
    journal, September 2015

    • Jiang, Shang-Da; Maganas, Dimitrios; Levesanos, Nikolaos
    • Journal of the American Chemical Society, Vol. 137, Issue 40
    • DOI: 10.1021/jacs.5b06716

    Comprehensive Spectroscopic Determination of the Crystal Field Splitting in an Erbium Single-Ion Magnet
    journal, September 2015

    • Rechkemmer, Yvonne; Fischer, Julia E.; Marx, Raphael
    • Journal of the American Chemical Society, Vol. 137, Issue 40
    • DOI: 10.1021/jacs.5b08344

    Organometallic Single-Molecule Magnets
    journal, January 2014


    Molecular magnetic hysteresis at 60 kelvin in dysprosocenium
    journal, August 2017

    • Goodwin, Conrad A. P.; Ortu, Fabrizio; Reta, Daniel
    • Nature, Vol. 548, Issue 7668
    • DOI: 10.1038/nature23447

    A four-coordinate cobalt(II) single-ion magnet with coercivity and a very high energy barrier
    journal, February 2016

    • Rechkemmer, Yvonne; Breitgoff, Frauke D.; van der Meer, Margarethe
    • Nature Communications, Vol. 7, Issue 1
    • DOI: 10.1038/ncomms10467

    Origin of slow magnetic relaxation in Kramers ions with non-uniaxial anisotropy
    journal, July 2014

    • Gómez-Coca, Silvia; Urtizberea, Ainhoa; Cremades, Eduard
    • Nature Communications, Vol. 5, Issue 1
    • DOI: 10.1038/ncomms5300

    Frequency domain Fourier transform THz-EPR on single molecule magnets using coherent synchrotron radiation
    journal, January 2009

    • Schnegg, Alexander; Behrends, Jan; Lips, Klaus
    • Physical Chemistry Chemical Physics, Vol. 11, Issue 31
    • DOI: 10.1039/b905745e

    Exploiting single-ion anisotropy in the design of f-element single-molecule magnets
    journal, January 2011

    • Rinehart, Jeffrey D.; Long, Jeffrey R.
    • Chemical Science, Vol. 2, Issue 11
    • DOI: 10.1039/c1sc00513h

    Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect
    journal, March 2005

    • Carver, Graham; Spichiger, David; Tregenna-Piggott, Philip L. W.
    • The Journal of Chemical Physics, Vol. 122, Issue 12
    • DOI: 10.1063/1.1872835

    Far infrared magnetic resonance in FeSiF 6 ⋅6H 2 O and Fe(SPh) 4 2−
    journal, March 1977

    • Champion, P. M.; Sievers, A. J.
    • The Journal of Chemical Physics, Vol. 66, Issue 5
    • DOI: 10.1063/1.434200

    Electronic structure and magnetic properties of high-spin octahedral Co(II) complexes: Co(II)(acac)2(H2O)2
    journal, December 1999

    • Lohr, Lawrence L.; Miller, Jeremy C.; Sharp, Robert R.
    • The Journal of Chemical Physics, Vol. 111, Issue 22
    • DOI: 10.1063/1.480365

    Far infrared spectra of magnetic ions in crystals
    journal, September 1972


    Chemical accuracy for the van der Waals density functional
    journal, December 2009

    • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
    • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
    • DOI: 10.1088/0953-8984/22/2/022201

    Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet
    journal, October 2018


    Magnetic hysteresis up to 80 kelvin in a dysprosium metallocene single-molecule magnet
    journal, October 2018