Theoretical study by DFT of organometallic complexes based on metallocenes active in NLO.

This study is based on the valuation of a few model molecules. The objective of this research is focused on linear optical (LO) and nonlinear optical (NLO) enhancement of five organometallic molecules based on different metallocenes. These molecules were subjected to several calculations by different long-range functionals CAM-B3LYP, LC-BLYP, LC-wPBE, wB97X, M11, and the following three Minnesota functionals: M06-2X and M08-HX in comparison with the MP2 approach. Hence, the CAM-B3LYP functional gave the closest NLO values to the MP2 method. Second, molecule 3A based on nickelocene recorded the highest static (ßtot) value which is 76.46 Χ 10-30 esu and 4803.4 Χ 10-30 esu under the laser wavelength λ = 532 nm. Third, intramolecular charge transfers (ICTs) of the molecules studied are all directed in both directions (donor to acceptor and vice versa). Finally, the specific solvent for molecules 2A and 3A is acetonitrile, and the maximum wavelengths obtained for the isolated or solvated molecule are all located in the near UV; the corresponding interval is between 250 and 395 nm. Graphical abstract.

Electronic and Vibrational Spectroscopy of CsS.

Using multi configurational ab initio methodologies, we compute the potential energy curves (PECs) of the lowest electronic states of the diatomic CsS. These computations are performed using internally contracted multireference interaction configuration including Davidson correction (MRCI+Q) with and without considering spin-orbit effects. The shapes of the PECs are governed by the interactions between the two ionic states, 2Σ+ and 2Π, correlating at large internuclear separations ( RCsS) to the first ionic dissociation limit and the other electronic states correlating to the three lowest neutral dissociation limits. Computations show the importance of considering a large amount of electron correlation for the accurate description of the PECs and spectroscopy of this molecular system. As expected, these PECs are also strongly affected by the spin-orbit interaction. For the bound states, we report a set of spectroscopic parameters including equilibrium distances, dissociation energies, and vibrational and rotational constants. The effects of spin-orbit-induced changes on these parameters are also discussed. Moreover, we show that the 22Π state presents a "bowl" potential with a rather flat region extending to large RCsS distances. After being promoted to this state, wavepackets should undergo strong oscillations, similar to those observed by Zewail and co-workers for the NaI molecule. These should provide information on the shape of the PEC for the 22Π state and also on the couplings between this and the neighboring states.