Quasi-two-dimensional magnetism and antiferromagnetic ground state in Li$_2$FeSiO$_4$

TL;DR

This study combines experimental and computational methods to reveal quasi-two-dimensional antiferromagnetic order in Li₂FeSiO₄, with magnetic correlations extending up to 200 K and a ground state consistent with 2D Ising behavior.

Contribution

It provides the first detailed experimental and theoretical investigation demonstrating the 2D magnetic nature and antiferromagnetic ground state of Li₂FeSiO₄.

Findings

Long-range antiferromagnetic order below 17 K.

Magnetic correlations extend up to 200 K.

Dominant in-plane magnetic exchange interactions.

Abstract

Our experimental (neutron diffraction, M\"ossbauer spectroscopy, magnetic susceptibility, specific heat) and numerical studies on the evolution of short- and long-range magnetic order in $\gamma_{\rm II}$-Li\(_2\)FeSiO\(_4\) suggest a quasi-two-dimensional (2D) nature of magnetism. The experimental data obtained on single crystals imply long-range antiferromagnetic order below $T_{\rm N}= 17$~K. A broad maximum in magnetic susceptibility $\chi$ at $T_{\rm m}\simeq 28$~K, observation of magnetic entropy changes up to 100~K and anisotropy in $\chi$ are indicative of low-dimensional magnetism and suggest short-range magnetic correlations up to 200~K. Neutron diffraction shows that long-range antiferromagnetic order is characterised by the propagation vector k=(1/2,0,1/2). The ordered moment $\mu = 2.50(2) \mu_B$ /Fe, at $T = 1.5$~K, is along the crystallographic $a$-axis. This is consistent with the observed static hyperfine field of $B_{\rm hyp}=14.8(3)$\,T by M\"ossbauer spectroscopy which indicates significant orbital contributions. The temperature dependence of $B_{\rm hyp}$ yields the critical exponent $\beta=0.116(12)$ which is in the regime of the 2D Ising behaviour. LSDA+U studies exploiting the experimental spin structure suggest dominating magnetic exchange coupling within the $ac$-layers (i.e., $J_3\simeq -6$~K and $J_6\simeq-2$~K) while interlayer coupling is much smaller and partly frustrated. This confirms the 2D nature of magnetism and is in full agreement with the experimental findings.