Field- and temperature-dependent quantum tunnelling of the magnetisation in a large barrier single-molecule magnet

Understanding quantum tunnelling of the magnetisation (QTM) in single-molecule magnets (SMMs) is crucial for improving performance and achieving molecule-based information storage above liquid nitrogen temperatures. Here, through a field- and temperature-dependent study of the magnetisation dynamics of [Dy(^tBuO)Cl(THF)₅][BPh₄]·2THF, we elucidate the different relaxation processes: field-independent Orbach and Raman mechanisms dominate at high temperatures, a single-phonon direct process dominates at low temperatures and fields >1 kOe, and a field- and temperature-dependent QTM process operates near zero field. Accounting for the exponential temperature dependence of the phonon collision rate in the QTM process, we model the magnetisation dynamics over 11 orders of magnitude and find a QTM tunnelling gap on the order of 10^-4 to 10^-5 cm^-1. We show that removal of Dy nuclear spins does not suppress QTM, and argue that while internal dipolar fields and hyperfine coupling support QTM, it is the dynamic crystal field that drives efficient QTM.