The datasets for ELNES/XANES and the corresponding ground-state PDOS were all generated using first-principles calculations based on DFT . Firstly, we retrieved all the structures of Si registered on the Materials Project , which resulted in 41 structures. Using the "SpaceGroupAnalyzer" class in the "pymatgen.symmetry" package , we searched for the primitive cell across all these structures and then enumerated all the inequivalent Si sites in all the Si structures, identifying 655 Si sites. To address the scarcity of data, data augmentation was conducted in an on-the-fly manner, ultimately yielding data for 1,405 Si sites. Detailed procedure for the data augmentation process is provided in Supplementary Material B.