Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

Duncan H. Moseley; Shelby E. Stavretis; Zhenhua Zhu; Mei Guo; Craig M. Brown; Mykhaylo Ozerov; Yongqiang Cheng; Luke L. Daemen; Rachael Richardson; Gary Knight; Komalavalli Thirunavukkuarasu; Anibal J. Ramirez-Cuesta; Jinkui Tang; Zi Ling Xue

doi:10.1021/acs.inorgchem.0c00523

Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

Duncan H. Moseley, Shelby E. Stavretis, Zhenhua Zhu, Mei Guo, Craig M. Brown, Mykhaylo Ozerov, Yongqiang Cheng, Luke L. Daemen, Rachael Richardson, Gary Knight, Komalavalli Thirunavukkuarasu, Anibal J. Ramirez-Cuesta, Jinkui Tang, Zi Ling Xue

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe₃)₂]₃ (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm^-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the ⁴I_15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm^-1, corresponding to transitions from the ground state, M_J = ±15/2, to the first three excited states, M_J = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.

Original language	English
Pages (from-to)	5218-5230
Number of pages	13
Journal	Inorganic Chemistry
Volume	59
Issue number	7
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00523
State	Published - Apr 6 2020

Funding

The authors acknowledge the financial support by the US National Science Foundation (CHE-1633870 and CHE-1900296 to Z.-L.X.), the U.S. Department of Navy HBCU/MI program (K.T.), 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. A portion of this work was performed at the National High Magnetic Field Laboratory which is supported by National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. Neutron scattering experiments were conducted at the VISION beamline at ORNL’s Spallation Neutron Source, which is supported by the Scientific User Facilities Division, Office of Basic Energy Sciences (BES), U.S. Department of Energy (DOE), under Contract No. DE-AC0500OR22725 with UT Battelle, LLC. The computing resources were made available through the VirtuES and the ICEMAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. The authors thank Dr. Dmitry Smirnov and Zhengguang Lu for assistance. The authors acknowledge the financial support by the US National Science Foundation (CHE-1633870 and CHE-1900296 to Z.-L.X.), the U.S. Department of Navy HBCU/MI program (K.T.), 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. A portion of this work was performed at the National High Magnetic Field Laboratory which is supported by National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. Neutron scattering experiments were conducted at the VISION beamline at ORNL's Spallation Neutron Source, which is supported by the Scientific User Facilities Division, Office of Basic Energy Sciences (BES), U.S. Department of Energy (DOE), under Contract No. DE-AC0500OR22725 with UT Battelle LLC. The computing resources were made available through the VirtuES and the ICEMAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL.

Funders	Funder number
Compute and Data Environment for Science
Office of Basic Energy Sciences
Scientific User Facilities Division
Shull Wollan Center
State of Florida
US National Science Foundation	CHE-1900296, CHE-1633870
UT Battelle LLC
National Science Foundation	DMR-1644779, 1900296
U.S. Department of Energy	DE-AC0500OR22725
Basic Energy Sciences
American Chemical Society Petroleum Research Fund
Laboratory Directed Research and Development
Cades Foundation
U.S. Navy

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10.1021/acs.inorgchem.0c00523

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Moseley, D. H., Stavretis, S. E., Zhu, Z., Guo, M., Brown, C. M., Ozerov, M., Cheng, Y., Daemen, L. L., Richardson, R., Knight, G., Thirunavukkuarasu, K., Ramirez-Cuesta, A. J., Tang, J., & Xue, Z. L. (2020). Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet. Inorganic Chemistry, 59(7), 5218-5230. https://doi.org/10.1021/acs.inorgchem.0c00523

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title = "Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet",

abstract = "Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.",

author = "Moseley, {Duncan H.} and Stavretis, {Shelby E.} and Zhenhua Zhu and Mei Guo and Brown, {Craig M.} and Mykhaylo Ozerov and Yongqiang Cheng and Daemen, {Luke L.} and Rachael Richardson and Gary Knight and Komalavalli Thirunavukkuarasu and Ramirez-Cuesta, {Anibal J.} and Jinkui Tang and Xue, {Zi Ling}",

note = "Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

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Moseley, DH, Stavretis, SE, Zhu, Z, Guo, M, Brown, CM, Ozerov, M, Cheng, Y, Daemen, LL, Richardson, R, Knight, G, Thirunavukkuarasu, K, Ramirez-Cuesta, AJ, Tang, J & Xue, ZL 2020, 'Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet', Inorganic Chemistry, vol. 59, no. 7, pp. 5218-5230. https://doi.org/10.1021/acs.inorgchem.0c00523

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T1 - Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

AU - Moseley, Duncan H.

AU - Stavretis, Shelby E.

AU - Zhu, Zhenhua

AU - Guo, Mei

AU - Brown, Craig M.

AU - Ozerov, Mykhaylo

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Richardson, Rachael

AU - Knight, Gary

AU - Thirunavukkuarasu, Komalavalli

AU - Ramirez-Cuesta, Anibal J.

AU - Tang, Jinkui

AU - Xue, Zi Ling

PY - 2020/4/6

Y1 - 2020/4/6

N2 - Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.

AB - Spin-phonon coupling plays a critical role in magnetic relaxation in single-molecule magnets (SMMs) and molecular qubits. Yet, few studies of its nature have been conducted. Phonons here refer to both intermolecular and intramolecular vibrations. In the current work, we show spin-phonon couplings between IR-active phonons in a lanthanide molecular complex and Kramers doublets (from the crystal field). For the SMM Er[N(SiMe3)2]3 (1, Me = methyl), the couplings are observed in the far-IR magnetospectroscopy (FIRMS) of crystals with coupling constants ≈ 2-3 cm-1. In particular, one of the magnetic excitations couples to at least two phonon excitations. The FIRMS reveals at least three magnetic excitations (within the 4I15/2 ground state/manifold; hereafter, manifold) at 0 T at 104, ∼180, and 245 cm-1, corresponding to transitions from the ground state, MJ = ±15/2, to the first three excited states, MJ = ±13/2, ±11/2, and ±9/2, respectively. The transition between the ground and first excited Kramers doublet in 1 is also observed in inelastic neutron scattering (INS) spectroscopy, moving to a higher energy with an increasing magnetic field. INS also gives complete phonon spectra of 1. Periodic DFT computations provide the energies of all phonon excitations, which compare well with the spectra from INS, supporting the assignment of the inter-Kramers doublet (magnetic) transitions in the spectra. The current studies unveil and measure the spin-phonon couplings in a typical lanthanide complex and throw light on the origin of the spin-phonon entanglement.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 7

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Inter-Kramers Transitions and Spin-Phonon Couplings in a Lanthanide-Based Single-Molecule Magnet

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