Crystal field and magnetism of Pr$^{3+}$ and Nd$^{3+}$ ions in orthorhombic perovskites

TL;DR

This paper calculates the crystal field parameters and magnetic properties of Pr$^{3+}$ and Nd$^{3+}$ ions in orthorhombic perovskites, achieving good agreement with experimental data and introducing a method with a single adjustable parameter.

Contribution

The study develops a method to compute crystal field parameters in rare-earth perovskites using Wannier functions with only one adjustable parameter, improving accuracy of energy level and magnetic property predictions.

Findings

Calculated energy levels match experimental data within a few meV.

Magnetic susceptibility calculations agree well with measurements.

Method provides reliable predictions for different RMO$_3$ compounds.

Abstract

Fifteen parameters characterizing the crystal field of rare-earth ions in the RMO$_3$ perovskites (R = Pr, Nd, M = Ga, Co) are calculated by expanding the local Hamiltonian expressed in the basis of Wannier functions into a series of spherical tensor operators. The method contains a single adjustable parameter that characterizes the hybridization of R($4f$) states with the states of oxygen ligands. Subsequently the energy levels and magnetic moments of trivalent R ion are determined by diagonalization of an effective Hamiltonian which, besides the crystal field, contains the $4f$ electron-electron repulsion, spin-orbit coupling and interaction with magnetic field. In the Ga compounds the energy levels of the ground multiplet agree within few meV with those determined experimentally by other authors. For all four compounds in question the temperature dependence of magnetic susceptibility is measured on polycrystalline samples and compared with the results of calculation. For NdGaO$_3$ theory is also compared with the magnetic measurements on a single crystal presented by Luis {\it et al.} Phys. Rev. B {\bf 58}, 798 (1998). A good agreement between the experiment and theory is found.