Spin–phonon Couplings in Transition Metal Complexes with Slow Magnetic Relaxation

Source Publication (e.g., journal title)

Nature Communications

Authors

Duncan H. Moseley, University of Tennessee, Knoxville
Shelby E. Stavretis, University of Tennessee, Knoxville
Komalavalli Thirunavukkuarasu, Florida A&M University
Mykhaylo Ozerov, National High Magnetic Field Laboratory
Yongqiang Cheng, Oak Ridge National Laboratory
Luke L. Daemen, Oak Ridge National Laboratory
Jonathan Ludwig, National High Magnetic Field Laboratory
Zhengguang Lu, National High Magnetic Field Laboratory
Dmitry Smirnov, National High Magnetic Field Laboratory
Craig M. Brown, National Institute of Standards and Technology
Anup Pandey, Oak Ridge National Laboratory
A. J. Ramirez-Cuesta, Oak Ridge National Laboratory
Adam C. Lamb, University of Tennessee, Knoxville
Mihail Atanasov, Max Planck Institute for Coal Research
Eckhard Bill, Max Planck Institute for Chemical Energy Conversion
Frank Neese, Max Planck Institute for Coal Research
Zi-Ling Xue, University of Tennessee, KnoxvilleFollow

Document Type

Article

Publication Date

7-3-2018

DOI

10.1038/s41467-018-04896-0

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.

Comments

This article was published openly thanks to the University of Tennessee Open Publishing Support Fund.

Licensed under a Creative Commons Attribution 4.0 International license.

Recommended Citation

Moseley, Duncan H., 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, and Zi-Ling Xue. “Spin–phonon Couplings in Transition Metal Complexes with Slow Magnetic Relaxation.” Nature Communications 9 (2018). https://doi.org/10.1038/s41467-018-04896-0.

Submission Type

Publisher's Version