Magnetism,exchange and crystal field parameters in the orbitally unquenched Ising antiferromagnet FePS3

FePS₃ is a layered antiferromagnet (T _N=123 K) with a marked Ising anisotropy in magnetic properties. The anisotropy arises from the combined effect of the trigonal distortion from octahedral symmetry and spin-orbit coupling on the orbitally degenerate⁵ T _2g ground state of the Fe²⁺ ion. The anisotropic paramagnetic susceptibilities are interpreted in terms of the zero field Hamiltonian, ℋ=Σ_i δ(L _iz ² −2)+|λ|L _i .S _i ]−Σ _ij J _ij S _i .S _j . The crystal field trigonal distortion parameter Δ, the spin-orbit coupling λ and the isotropic Heisenberg exchange,J _ij, were evaluated from an analysis of the high temperature paramagnetic susceptibility data using the Correlated Effective Field (CEF) theory for many-body magnetism developed by Lines. Good agreement with experiment were obtained for Δ/k=215.5 K; λ/k=166.5 K;J _nn k=27.7 K; andJ _nnn k=−2.3 K. Using these values of the crystal field and exchange parameters the CEF predicts aT _N=122 K for FePS₃, which is remarkably close to the observed value of theT _N. The accuracy of the CEF approximation was also ascertained by comparing the calculated susceptibilities in the CEF with the experimental susceptibility for the isotropic Heisenberg layered antiferromagnet MnPS₃, for which the high temperature series expansion susceptibility is available.