Improving excited-state dynamic properties with the help of metalide character and excess electrons: earlier transition-metal pairing with superalkali clusters
Abstract
Recognizing the increased stability of metalide complexes over alkali anions, research on transition metal-based metalides continues to grow. Here, employing various quantum chemical methods, we investigate novel superalkali-M (where M = Sc, Ti, V, Cr, and Mn) pairings theoretically, and our results indicate that the excited-state dynamic properties of these complexes are enhanced due to their metalide character and excess electrons. In the designed Li3O@[12-crown-4]M complexes, Li3O demonstrates excellent charge transfer through van der Waals (vdW) interactions. Ab initio molecular dynamic simulations demonstrate their kinetic and dynamic stabilities, and the thermodynamics of physisorption is also unveiled. A remarkable hyperpolarizability value of 7.6 × 105 a.u. is observed for the Sc complex, while the hyper-Rayleigh scattering value is highest for the Mn complex. The influence of different solvents on the hyperpolarizability response is thoroughly investigated. Moreover, dynamic NLO parameters are computed using various externally applied frequencies. The nature of bonding and the role of vdW interactions in triggering NLO responses are unveiled. In addition to the infrared analysis, the effect of vertical excitation energy has also been investigated in enhancing dynamic NLO features. We hope that these findings hold promise for advancing NLO applications of organic functional materials.
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