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Ab Initio Prediction of High-Temperature Magnetic Relaxation Rates in Single-Molecule Magnets

preprint
submitted on 19.01.2021, 10:52 and posted on 20.01.2021, 09:16 by Daniel Reta, Jon G. C. Kragskow, Nicholas Chilton

Organometallic molecules based on [Dy(CpR)2]+ cations have emerged as clear front-runners in the search for high-temperature single-molecule magnets. However, despite a growing family of structurally-similar molecules, these molecules show significant variations in their magnetic properties, demonstrating the importance of understanding magneto-structural relationships towards developing more efficient design strategies. Here we refine our ab initio spin dynamics methodology and show that it is capable of quantitative prediction of relative relaxation rates in the Orbach region. Applying it to all reported [Dy(CpR)2]+ cations allows us to tease out differences in their relaxation dynamics, highlighting that the main discriminant is the magnitude of the crystal field splitting. We subsequently employ the method to predict relaxation rates for a series of hypothetical organometallic sandwich compounds, revealing an upper limit to the effective barrier to magnetic relaxation of around 2200 K, which has been reached. However, we show that further improvements to single-molecule magnets can be made by moving vibrational modes off-resonance with electronic excitations.

Funding

EPSRC

ERC-2019-STG-851504

Royal Society

History

Email Address of Submitting Author

nicholas.chilton@manchester.ac.uk

Institution

The University of Manchester

Country

United Kingdom

ORCID For Submitting Author

0000-0002-8604-0171

Declaration of Conflict of Interest

No conflict of interest

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