Second-order transverse magnetic anisotropy induced by disorders in the single-molecule magnet Mn12

TL;DR

This study uses density-functional theory to analyze how solvent-induced positional and orientational disorders in Mn12 single-molecule magnets influence second-order transverse magnetic anisotropy, aligning theoretical predictions with experimental observations.

Contribution

It provides a detailed computational analysis of disorder effects on magnetic anisotropy in Mn12, clarifying the role of solvent interactions and geometric relaxations.

Findings

Hydrogen bonding with solvent molecules significantly increases the E value.

Geometry relaxation enhances the calculated E value.

Largest E value found is 0.016 K, comparable to experiments.

Abstract

For the single-molecule magnet Mn12, Cornia et al. recently proposed that solvent molecules may cause the quantum tunneling that requires a lower symmetry than S4. However, magnetic quantum tunneling and electron paramagnetic resonance experiments suggested that the proposed theory may not correspond to the measurements. In this regard, we consider positional disorder induced by the solvent molecules and orientational disorder by the methyl groups of a Mn12 molecule. We calculate, within density-functional theory, the second-order transverse magnetic anisotropy parameter E and an easy-axis tilting angle induced by the positional disorder and the E value by the orientational disorder. We also calculate the local magnetic anisotropy and the local easy axis for each inequivalent Mn site in different environments to investigate their effects on the global E value. We find that the hydrogen bonding between a Mn12 molecule and the solvent molecule is crucial to obtain a substantial E value and that the E value increases upon geometry relaxations. Our calculations on relaxed geometries show that the largest calculated E value is 0.016 K and that the largest tilting angle is 0.5 degrees. Our largest E value is comparable to experimental results but larger than Cornia et al.'s.