A study of transition metal K-edge x-ray absorption spectra of LaBO3 (B=Mn, Fe, Co, Ni), La2CuO4 and SrMnO3 using partial density of states

TL;DR

This study combines experimental and theoretical analysis of transition metal K-edge XANES spectra in various LaBO3 compounds, revealing that single-particle transitions within LDA are sufficient to explain observed spectral features mainly due to TM 4p DOS hybridization.

Contribution

The paper demonstrates that LDA-based single-particle calculations can accurately reproduce XANES spectra, emphasizing the role of hybridization over many-body effects, and explores the impact of Coulomb and exchange interactions.

Findings

Experimental and theoretical spectra show good agreement.

Features are mainly due to TM 4p DOS hybridization.

U corrections influence spectral detail but not new features.

Abstract

The transition metal K-edge x-ray absorption near edge structure (XANES) studies have been carried on LaBO3 (B=Mn, Fe, Co, Ni), La2CuO4 and SrMnO3 compounds. The theoretical spectra have been calculated using transition metal (TM) 4p density of states (DOS) obtained from full-potential LMTO density functional theory. The exchange-correlation functional used in this calculation is taken under local density approximation (LDA). The comparison of experimental spectra with the calculated ones indicates that single-particle transitions under LDA are sufficient to generate all the observed XANES including those which have earlier been attributed to many-body shake-up transitions and core-hole potentials. The present study reveals that all the experimentally observed features are mainly due to distribution in TM 4p DOS influenced by hybridization with other orbitals. Specifically, for LaMnO3, the feature earlier attributed to shake-up process is seen to arise from hybridization of Mn 4p with La 6p and O 2p orbitals; in La2CuO4 the features attributed to core hole potential correspond to hybridization of Cu 4p with La 6p, La 5d and O 2p orbitals. To see the effect of inhomogeneous electronic charge distribution and on-site Coulomb and exchange interaction (U) on the XANES of these compounds generalized-gradient approximation and U corrections are incorporated in the calculations. These corrections do not generate any new features in the spectra but affect the detailed intensity and positions of some of the features.