The Local Electronic Structure of Supercritical CO₂ from X-ray Raman Spectroscopy and Atomistic-Scale Modeling

Supercritical CO₂ is encountered in several technical and natural systems related to biology, geophysics, and engineering. While the structure of gaseous CO₂ has been studied extensively, the properties of supercritical CO₂, particularly close to the critical point, are not well-known. In this work, we combine X-ray Raman spectroscopy, molecular dynamics simulations, and first-principles density functional theory (DFT) calculations to characterize the local electronic structure of supercritical CO₂ at conditions around the critical point. The X-ray Raman oxygen K-edge spectra manifest systematic trends associated with the phase change of CO₂ and the intermolecular distance. Extensive first-principles DFT calculations rationalize these observations on the basis of the 4sσ Rydberg state hybridization. X-ray Raman spectroscopy is found to be a sensitive tool for characterizing electronic properties of CO₂ under challenging experimental conditions and is demonstrated to be a unique probe for studying the electronic structure of supercritical fluids.