XANES Absorption Spectra of Penta-Graphene and Penta-SiC2 with Different Terminations: A Computational Study

Pentagonal two-dimensional allotropes—penta-graphene (PG) and penta-SiC2—are promising but experimentally elusive materials whose identification requires spectroscopic fingerprints that extend beyond ground-state descriptors. Using density functional theory within a core-hole formalism and polarisation-resolved cross sections, we compute element- and site-resolved K-edge spectra for pristine H- and OH-terminated PG, Si-substituted PG, and pristine/H-passivated penta-SiC2. In PG, the C K-edge shows a 𝜋* onset at 285 eV from three-coordinated C and 𝜎* bands at 293–303 eV, yielding three plateaus and a strong low-energy z-polarised response. The H/OH functionalisation suppresses the 283–288 eV plateau and weakens the polarisation anisotropy, which can be rationalised by PDOS changes at the two non-equivalent C sites. Si substitution generates a polarisation-dependent Si K-edge doublet (∼1844/1857 eV). In penta-SiC2, the high-energy Si feature broadens (1850–1860 eV) and the C K-edge becomes strongly anisotropic; H-passivation yields a sharp, almost polarisation-independent C K-edge at 290 eV. The presence of clearly resolved, system-dependent spectral features enables unambiguous experimental discrimination between phases and terminations, facilitating spectroscopic discovery and supporting device development in 2D pentagonal materials.