Effect of Internal Donors on Raman and IR Spectroscopic Fingerprints of MgCl(2)/TiCl(4) Nanoclusters Determined by Machine Learning and DFT

To go deep into the origin of MgCl [Formula: see text] supported Ziegler-Natta catalysis we need to fully understand the structure and properties of precatalytic nanoclusters MgCl [Formula: see text] /TiCl [Formula: see text] in presence of Lewis bases as internal donors (ID). In this work MgCl [Formula: see text] /TiCl [Formula: see text] nanoplatelets derived by machine learning and DFT calculations have been used to model the interaction with ethyl-benzoate EB as ID, with available exposed sites of binary Ti [Formula: see text] Cl [Formula: see text] /MgCl [Formula: see text] systems. The influence of vicinal Ti [Formula: see text] Cl [Formula: see text] and coadsorbed TiCl [Formula: see text] on energetic, structural and spectroscopic behaviour of EB has been considered. The adsorption of homogeneous-like TiCl [Formula: see text] EB and TiCl [Formula: see text] (EB) [Formula: see text] at the various surface sites have been also simulated. B3LYP-D2 and M06 functionals combined with TZVP quality basis set have been adopted for calculations. The adducts have been characterized by computing IR and Raman spectra that have been found to provide specific fingerprints useful to identify surface species; IR spectra have been successfully compared to available experimental data.