Unveiling the structure of chlorine-doped graphdiyne via first-principles X-ray spectroscopy

Abstract

Chlorine-doped graphdiyne (Cl-GDY) exhibits exceptional properties, demonstrating significant potential for application in energy storage, conversion and electrocatalysis. However, systematic investigations of the structural configurations of Cl-GDY remain scarce, both experimentally and theoretically. In this work, we selected five canonical Cl-GDY configurations along with pristine GDY and simulated their C 1s and Cl 2p X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra. The calculated C 1s ionization potentials (IPs) show good agreement with the experimental XPS, hence all feature peaks in experimental XPS were assigned. Furthermore, we established robust structure–spectrum relationships in which distinct doping configurations can be identified from theoretical NEXAFS spectral profiles and peak positions. This study provides critical theoretical benchmarks for differentiating Cl-GDY configurations, bridging computational insights with experimental characterization.