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

20 January 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

single-molecule magnet
magnetic relaxation dynamics

Supplementary materials

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