LAUSR

Abstract The structural, thermodynamic and spectral properties of photocatalytically active composite copolymers of polytitaniumoxide and hydroxyethyl methacrylate TiO2/HEMA and the copolymers with incorporated gold nanoparticles (AuNPs) TiO2/HEMA/Au have been studied using the DFT and TD-DFT theories (B3LYP/LANL08(Au)/6-31G(d,p)). Molecular clusters of TiO2 with the chemically linked residues of HEMA were considered as copolymer models containing various structure motifs, such as linear chains, double bonds, tetrahedral, cubic and octahedral TiO2 fragments. The AuNPs incorporation was modeled by Au atoms and Au7 clusters coordinated at various positions of the TiO2/HEMA copolymer. The effect of cluster structure and Au coordination modes on thermodynamic characteristics, IR spectra, electronic excitation spectra and the photoinduced electron redistribution has been analyzed on the basis of comparison with the experimental IR and UV spectra. The results demonstrate the influence of various structural features and NP coordination modes on photocatalytic properties, which is important for the synthesis of copolymers with required characteristics.