Investigation of the multiplet features of SrTiO3 in X‐ray absorption spectra based on configuration interaction calculations

Synchrotron‐based L2,3‐edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here, using the experimental Ti L2,3‐edges absorption spectrum of SrTiO3 as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L3 and L2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature are further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non‐linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO3‐based thin films and heterostructures is offered. Detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the eg crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties. Configuration interaction cluster calculations are a powerful tool for understanding the multiplet structures of the Ti L2,3‐edges absorption spectrum of SrTiO3 which yields different energy parameters representing the ground state properties. Simulated absorption spectra with different linearly polarized photons under various tetragonal crystal fields reveal a non‐linear orbital–lattice interaction, which, in combination with a detailed analysis of the spectral shifts in different tetragonal crystal fields, offers a theoretical guidance for material engineering of SrTiO3‐based thin films and heterostructures.