Magnetism based on nitrate-nitrate interactions: The cases of LiNO$_3$, K$_{0.5}$Rb$_{0.5}$NO$_3$, Ca(NO$_3$)$_2$ and C(NH$_2$)$_3$NO$_3$

TL;DR

This study reveals long-range magnetic ordering in nitrate salts caused by orbital interactions of NO$_3^-$ ions, leading to antiferromagnetic structures and phase transitions, with implications for energy storage materials.

Contribution

It uncovers a novel magnetic ordering mechanism in nitrate salts based on nitrate-nitrate interactions, expanding understanding of molecular magnetism.

Findings

Long-range magnetic ordering observed in nitrate salts.

Phase transitions are first order with hysteresis.

Nitrate-nitrate interactions induce antiferromagnetic structure.

Abstract

Long-range magnetic ordering of the orbital motion of oxygen atoms within NO$_3$$^-$ cations is identified from experimental measurements of the magnetic susceptibility $\chi$($T$) in LiNO$_3$, Ca(NO$_3$)$_2$, K$_{0.5}$Rb$_{0.5}$NO$_3$ and C(NH$_2$)$_3$NO$_3$ at their respective order-disorder, solid-solid phase transitions $T$$_N$. The observed sharp changes in $\chi$($T$) and accompanying hysteretic behavior indicate the phase transitions to be first order. A model employing the law of conservation of angular momentum is used to explain why the librations between neighboring NO$_3$$^-$ become geared below $T$$_N$. Since the periodic motions involve concerted motion of net charges, the associated magnetic moments of the NO$_3$$^-$ ions indirectly establish an antiferromagnetic structure below $T$$_N$. Our findings identify a previously unidentified type of molecular interaction which may be exploited to further increase the enthalpy of the widely-popular hydrated salts employed as energy storage devices.