Spin-phonon couplings in transition metal complexes with slow magnetic relaxation

Duncan H. Moseley; Shelby E. Stavretis; Komalavalli Thirunavukkuarasu; Mykhaylo Ozerov; Yongqiang Cheng; Luke L. Daemen; Jonathan Ludwig; Zhengguang Lu; Dmitry Smirnov; Craig M. Brown; Anup Pandey; A. J. Ramirez-Cuesta; Adam C. Lamb; Mihail Atanasov; Eckhard Bill; Frank Neese; Zi Ling Xue

doi:10.1038/s41467-018-04896-0

Spin-phonon couplings in transition metal complexes with slow magnetic relaxation

Duncan H. Moseley, Shelby E. Stavretis, Komalavalli Thirunavukkuarasu, Mykhaylo Ozerov, Yongqiang Cheng, Luke L. Daemen, Jonathan Ludwig, Zhengguang Lu, Dmitry Smirnov, Craig M. Brown, Anup Pandey, A. J. Ramirez-Cuesta, Adam C. Lamb, Mihail Atanasov, Eckhard Bill, Frank Neese, Zi Ling Xue

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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, we show for the first time distinct couplings of g phonons of Co^II(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. 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.

Original language	English
Article number	2572
Journal	Nature Communications
Volume	9
Issue number	1
DOIs	https://doi.org/10.1038/s41467-018-04896-0
State	Published - Dec 1 2018

Funding

The authors thank financial support by the US National Science Foundation (CHE-1633870 to Z-L.X.), U.S. Department of Navy HBCU/MI program (K.T.), Deutsche Forschungsgemeinschaft and Max-Planck-Gesellschaft (M.A., E.B. and F.N.), and a Shull Wollan Center Graduate Research Fellowship (S.E.S). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this work. Computational resources for the VASP DFT calculations were made available through the VirtuES and ICE-MAN projects, funded by the Laboratory Directed Research and Development at Oak Ridge National Laboratory. The NHMFL is supported by NSF through NSF-DMR-0084173 and the State of Florida. Partial funding for open access to this article was provided by the University of Tennessee\u2019s Open Publishing Support Fund. Z-L.X. thanks Michael O. Yokosuk, Ryan A. Wallace, and Profs. Janice L. Musfeldt and Michael J. Sepaniak for their help.

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Moseley, D. H., Stavretis, S. E., Thirunavukkuarasu, K., Ozerov, M., Cheng, Y., Daemen, L. L., Ludwig, J., Lu, Z., Smirnov, D., Brown, C. M., Pandey, A., Ramirez-Cuesta, A. J., Lamb, A. C., Atanasov, M., Bill, E., Neese, F., & Xue, Z. L. (2018). Spin-phonon couplings in transition metal complexes with slow magnetic relaxation. Nature Communications, 9(1), Article 2572. https://doi.org/10.1038/s41467-018-04896-0

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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, 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. 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.",

author = "Moseley, {Duncan H.} and Stavretis, {Shelby E.} and Komalavalli Thirunavukkuarasu and Mykhaylo Ozerov and Yongqiang Cheng and Daemen, {Luke L.} and Jonathan Ludwig and Zhengguang Lu and Dmitry Smirnov and Brown, {Craig M.} and Anup Pandey and Ramirez-Cuesta, {A. J.} and Lamb, {Adam C.} and Mihail Atanasov and Eckhard Bill and Frank Neese and Xue, {Zi Ling}",

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Moseley, DH, Stavretis, SE, Thirunavukkuarasu, K, Ozerov, M, Cheng, Y, Daemen, LL, Ludwig, J, Lu, Z, Smirnov, D, Brown, CM, Pandey, A, Ramirez-Cuesta, AJ, Lamb, AC, Atanasov, M, Bill, E, Neese, F & Xue, ZL 2018, 'Spin-phonon couplings in transition metal complexes with slow magnetic relaxation', Nature Communications, vol. 9, no. 1, 2572. https://doi.org/10.1038/s41467-018-04896-0

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T1 - Spin-phonon couplings in transition metal complexes with slow magnetic relaxation

AU - Moseley, Duncan H.

AU - Stavretis, Shelby E.

AU - Thirunavukkuarasu, Komalavalli

AU - Ozerov, Mykhaylo

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Ludwig, Jonathan

AU - Lu, Zhengguang

AU - Smirnov, Dmitry

AU - Brown, Craig M.

AU - Pandey, Anup

AU - Ramirez-Cuesta, A. J.

AU - Lamb, Adam C.

AU - Atanasov, Mihail

AU - Bill, Eckhard

AU - Neese, Frank

AU - Xue, Zi Ling

PY - 2018/12/1

Y1 - 2018/12/1

N2 - 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, 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. 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.

AB - 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, 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. 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.

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VL - 9

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Spin-phonon couplings in transition metal complexes with slow magnetic relaxation

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