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

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 Co II(acac) 2(H 2O) 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:
Grant/Contract Number:
AC05-00OR22725
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
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE; National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1468922

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., 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. 2018. "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}
}

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