Ionicity and birefringence of α-LiNH4SO4 crystals: ab initio DFT study, X-ray spectroscopy measurements

Abstract

The structural, electronic properties and ionicity of the lithium ammonium sulfate dielectric crystals are examined using a complex approach including experimental studies of X-ray spectroscopy and the first principles band structure techniques within a framework of local electron density functional theory (DFT). Band energy dispersion, density of electronic states and dielectric function dispersion in the wide spectral range corresponding to electronic excitations were calculated using the plane wave basis and Vanderbilt ultra-soft pseudopotentials. The origin of the energy bands are estimated using density of states diagrams and the band gap magnitudes for different exchange correlation functions. To verify the data of the performed band structure calculations, the X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES) are used. The XPS core-level and valence-band spectra as well as the XES bands representing the energy distribution of the O 2p and N 2p states are studied. Theoretical refractive indices dispersion for the main crystallographic directions (n_a, n_b and n_c) as well as birefringence spectral dependences (Δn_a, Δn_b and Δn_c) in the visible spectral range are obtained. All the calculated properties are compared with the available experimental results and good agreement between both sets of data is demonstrated.