Design of high-temperature f-block molecular nanomagnets through the control of vibration-induced spin relaxation

TL;DR

This paper introduces a cost-effective first-principles method for evaluating vibration-induced spin relaxation in molecular f-block nanomagnets, aiding the design of high-temperature single-ion magnets by guiding ligand modifications.

Contribution

The paper presents a novel, computationally efficient approach requiring only one CASSCF calculation to predict spin relaxation, facilitating rational design of nanomagnets.

Findings

The method accurately evaluates vibration-induced spin relaxation.

Chemical modifications can suppress spin relaxation.

Potential to increase operational temperature of nanomagnets.

Abstract

One of the main roadblocks that still hampers the practical use of molecular nanomagnets is their cryogenic working temperature. In the pursuit of rational strategies to design new molecular nanomagnets with increasing blocking temperature, ab initio methodologies play an important role by guiding synthetic efforts at the lab stage. Nevertheless, when evaluating vibration-induced spin relaxation, these methodologies are still far from being computationally fast enough to provide a useful predictive framework. Herein, we present an inexpensive first-principles method devoted to evaluating vibration-induced spin relaxation in molecular f-block single-ion magnets, with the important advantage of requiring only one CASSCF calculation. We use a case study to illustrate the method, and propose chemical modifications in the ligand environment with the aim of suppressing spin relaxation.