A Hirshfeld charge analysis was also performed for the TiCl4 species, as it can influence active site properties such as regiospecificity and the ease of chain transfer reactions (Figure ). Without ID, {110} mononuclear species carried a negative charge ranging from 0 to -0.05, while {100} dinuclear species stood closer to neutral, and {100} mononuclear species was positively charged around +0.1. The addition of donors increased the negativity in all TiCl4 species due to their Lewis basicity, aligning with previous DFT calculations as well as experimental data. The effect was more pronounced for DEP, given the higher electron donating capability of the carbonyl group compared to the ether group in DE. Remarkably, a broad distribution of charges was observed within the same species, stemming from variations in the local environment around each TiCl4. This variation in charges within similar species would partly explain the multisite nature of the catalysts, and can provide a novel explanation to experimental IR spectra of phthalate-containing ZN catalysts, as detailed in the next section.