Modeling of the spectroscopy of core electrons with density functional theory

The availability of X-ray light sources with increased resolution and intensity has provided a foundation for increasingly sophisticated experimental studies exploiting the spectroscopy of core electrons to probe fundamental chemical, physical, and biological processes. Quantum chemical calculations can play a critical role in the analysis of these experimental measurements. The relatively low computational cost of density functional theory (DFT) and time-dependent density functional theory (TDDFT) make them attractive choices for simulating the spectroscopy of core electrons. An overview of current developments to apply DFT and TDDFT to study the key techniques of X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, X-ray emission spectroscopy, and resonant inelastic X-ray scattering is presented. Insight into the accuracy that can be achieved, in conjunction with an examination of the limitations and challenges to modeling the spectroscopy of core electrons with DFT is provided. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy Electronic Structure Theory > Density Functional Theory

Automated summary

The availability of X-ray light sources with increased resolution and intensity has provided a foundation for increasingly sophisticated experimental studies exploiting the spectroscopy of core electrons to probe fundamental chemical, physical, and biological processes. Quantum chemical calculations, particularly density functional theory (DFT) and time-dependent density functional theory (TDDFT), play a critical role in the analysis of experimental measurements. Current developments in applying DFT and TDDFT to study key X-ray spectroscopy techniques are presented, along with insights into the achievable accuracy and challenges in modeling core electron spectroscopy with DFT.