Isotope Effect on the Magnetic Properties of Hexamethylbenzene: Evidence of Magnetism Based on Correlated Motion of Deuterons

TL;DR

This study investigates isotope effects on the magnetic properties of hexamethylbenzene, revealing correlated deuteron motion and quantum tunneling phenomena, with implications for understanding molecular magnetism and isotope influence.

Contribution

It provides new magnetic susceptibility measurements on single crystals and demonstrates isotope-dependent anomalies, highlighting the role of deuterons in magnetic behavior.

Findings

Metastable behavior near 118 K in hydrogenated samples

Deuterated samples show anomalies at 132 K

Evidence of quantum tunneling of deuterons at 42 K

Abstract

The associated magnetic moments of the periodic rotational motion of methyl groups in hexamethylbenzene C$_6$(CH$_3$)$_6$ were recently identified to contribute to its overall magnetic susceptibility. Those measurements however, were only performed on hydrogenous polycrystalline samples. We report magnetic susceptibility measurements on single crystalline C$_6$(CH$_3$)$_6$ in the cases where the applied magnetic field is parallel and perpendicular to the molecular basal planes. In the former case, metastable behavior near the onset temperature T$_{C-H}$=118 K is identified while in the latter, no anomalous behavior is observed. Similar anomalies are observed in deuterated hexamethylbenzene C$_6$(CD$_3$)$_6$ (where D is deuterium), however, T$_{C-D}$ occurs 14 K higher at 132 K. In addition, a peak anomaly identified near 42 K is suggested to be due to the onset of coherent quantum tunneling of deuterons. The near cubic ground state is proposed to be the result of a more radical form of the Jahn-Teller effect occurring in a molecular solid where the lattice distorts to remove the orbital degeneracies of the protons to lower its energy. The apparent magnetic anisotropy and isotope effect provide evidence that apart from electrons, not only protons, but also deuterons establish strongly correlated behavior.