A Complete <i>Ab Initio</i> View of Orbach and Raman Spin–Lattice Relaxation in a Dysprosium Coordination Compound
Matteo Briganti, Fabio Santanni, Lorenzo Tesi, Federico Totti, Roberta Sessoli, Alessandro Lunghi
Abstract
and unveil the nature of all spin-phonon relaxation mechanisms, namely Orbach and Raman pathways, in a prototypical Dy single-molecule magnet. Computational predictions are in agreement with the experimental determination of spin relaxation time and crystal field anisotropy, and show that Raman relaxation, dominating at low temperature, is triggered by low-energy phonons and little affected by further engineering of crystal field axiality. A comprehensive analysis of spin-phonon coupling mechanism reveals that molecular vibrations beyond the ion's first coordination shell can also assume a prominent role in spin relaxation through an electrostatic polarization effect. Therefore, this work shows the way forward in the field by delivering a novel and complete set of chemically sound design rules tackling every aspect of spin relaxation at any temperature.