Research Information System
Results in Physics, vol.77, 2025 (SCI-Expanded)
In this study, we present a comprehensive first-principles investigation into the structural, electronic, optical, magnetic, and hyperfine properties of olivine-type LiMPO4 compounds (M =Co, Fe, Mg, Mn), using the full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). All compounds crystallize in the orthorhombic Pnma space group, with structural parameters exhibiting systematic variation according to the ionic radius of the M−site cation. Electronic band structure analysis reveals insulating behavior in LiFePO4 and LiMgPO4 with wide band gap, while LiCoPO4 and LiMnPO4 are identified as wide-bandgap semiconductors, owing to transition metal 3d–O 2p hybridization. Optical studies demonstrate pronounced anisotropy in dielectric response and absorption spectra, with LiMgPO4 exhibiting the highest absorption threshold. Spin-polarized calculations unveil high-spin magnetic configurations in transition-metal-based compounds, with total cell magnetic moments. Furthermore, hyperfine interaction analysis, including electric field gradients and magnetic shielding tensors, and highlights significant anisotropy effects, particularly for Fe2+ and Mn2+ centers. The quadrupole coupling constants (CQ) and asymmetry parameters (η) provide insights into local symmetry breaking and electron density distribution around metal centers. This integrated computational approach underscores the tunability of LiMPO4 compounds for next-generation lithium-ion battery cathodes and multifunctional materials with optoelectronic and magnetic properties.