Atomic multiplet and charge-transfer screening effects in 1$s$ and 2$p$ core-level X-ray photoelectron spectra of early 3$d$ transition-metal oxides

Abstract

We present a comparative analysis of 1$s$ and 2$p$ core-level hard X-ray photoelectron spectroscopy (HAXPES) spectra in metallic VO$_2$ and CrO$_2$. Even though the V 1$s$ and 2$p$ spectra in VO$_2$ display similar line shapes except the absence or presence of a spin-orbit coupling splitting, the Cr 1$s$ and 2$p$ spectra exhibit distinct main-line shapes. The experimental HAXPES spectra are analyzed by the Anderson impurity model based on the density functional theory + dynamical mean-field theory and a conventional MO$_6$ cluster model. We elucidate the complex interplay between formation of the intra-atomic multiplet and charge transfer effect on the chemical bonding followed by the 1$s$ and 2$p$ core electron excitations. We demonstrate the advantage of the 1$s$ excitations to the routinely-employed 2$p$ excitations for distinguishing between metal-ligand and metal-metal charge transfer contributions in early 3$d$ transition-metal oxides.