Origin and spectroscopic determination of trigonal anisotropy in a heteronuclear single-molecule magnet

TL;DR

This study uses high-resolution W-band EPR spectroscopy to accurately determine trigonal transverse magnetic anisotropy in a Fe3Cr single-molecule magnet, revealing structural influences on its quantum tunneling behavior.

Contribution

It provides the first spectroscopic determination of trigonal transverse anisotropy in a SMM, linking it to the cluster's structural features and advancing understanding of spin dynamics.

Findings

Identification of trigonal transverse magnetic anisotropy terms.

Correlation between anisotropy and cluster structure.

Implications for quantum tunneling and spin dynamics.

Abstract

W-band ({\nu} ca. 94 GHz) electron paramagnetic resonance (EPR) spectroscopy was used for a single-crystal study of a star-shaped Fe3Cr single-molecule magnet (SMM) with crystallographically imposed trigonal symmetry. The high resolution and sensitivity accessible with W-band EPR allowed us to determine accurately the axial zero-field splitting terms for the ground (S =6) and first two excited states (S =5 and S =4). Furthermore, spectra recorded by applying the magnetic field perpendicular to the trigonal axis showed a pi/6 angular modulation. This behavior is a signature of the presence of trigonal transverse magnetic anisotropy terms whose values had not been spectroscopically determined in any SMM prior to this work. Such in-plane anisotropy could only be justified by dropping the so-called 'giant spin approach' and by considering a complete multispin approach. From a detailed analysis of experimental data with the two models, it emerged that the observed trigonal anisotropy directly reflects the structural features of the cluster, i.e., the relative orientation of single-ion anisotropy tensors and the angular modulation of single-ion anisotropy components in the hard plane of the cluster. Finally, since high-order transverse anisotropy is pivotal in determining the spin dynamics in the quantum tunneling regime, we have compared the angular dependence of the tunnel splitting predicted by the two models upon application of a transverse field (Berry-phase interference).