Effects of structural variations to x-ray absorption spectra of g-C3N4: Insight from DFT and TDDFT simulations

X-ray absorption spectroscopy (XAS) is widely employed for structure characterization of graphitic carbon nitride (g-C3N4) and its composites. Nevertheless, even for pure g-C3N4, discrepancies in energy and profile exist across different experiments, which can be attributed to variations in structures arising from diverse synthesis conditions and calibration procedures. Here, we conducted a theoretical investigation on XAS of three representative g-C3N4 structures (planar, corrugated, and micro-corrugated) optimized with different strategies, to understand the structure–spectroscopy relation. Different methods were compared, including density functional theory (DFT) with the full core-hole (FCH) or equivalent core-hole (ECH) approximation as well as the time-dependent DFT (TDDFT). FCH was responsible for getting accurate absolute absorption energy; while ECH and TDDFT aided in interpreting the spectra, through ECH-state canonical molecular orbitals (ECH-CMOs) and natural transition orbitals (NTOs), respectively. With each method, the spectra at the three structures show evident differences, which can be correlated with different individual experiments or in between. Our calculations explained the structural reason behind the spectral discrepancies among different experiments. Moreover, profiles predicted by these methods also displayed consistency, so their differences can be used as a reliable indicator of their accuracy. Both ECH-CMOs and NTO particle orbitals led to similar graphics, validating their applicability in interpreting the transitions. This work provides a comprehensive analysis of the structure-XAS relation for g-C3N4, provides concrete explanations for the spectral differences reported in various experiments, and offers insight for future structure dynamical and transient x-ray spectral analyses.