Theoretical study of new push–pull molecules based on transition metals for NLO applications and determination of ICT mechanisms by DFT calculations

This study is based on the valuation of a few model molecules. The objective of this research is focussed on the nonlinear optical (NLO) improvement of four organometallic molecules and one organic molecule. These molecules have been subjected to several calculations by different functionals: CAM–B3LYP, LC–BLYP, LC–wPBE, wB97X, M11, M06–2X, M08–HX and M08–SO. These functionals gave three orders of classification of the [Formula: see text] parameters. The CAM–B3LYP functional recorded very good agreement between [Formula: see text] parameters and gaps ([Formula: see text]. Significant first hyperpolarizabilities ([Formula: see text] have been obtained around 880 * 10[Formula: see text][Formula: see text]esu. The mechanisms of intramolecular charge transfer (ICT) have shown energetic passages from donor groups to acceptors and vice versa. The substitution of metals influences the location of [Formula: see text] electrons at the level of the chromophores. Finally, the lengthening of the aromatic chains between the acceptor and donor groups shows significant NLO improvements. The first and second hyperpolarizabilities ([Formula: see text] and ([Formula: see text] for a chain of several benzene rings are of the order of 21,663.16 * 10[Formula: see text][Formula: see text]esu and 16,464.65 * 10[Formula: see text][Formula: see text]esu, respectively.