Engineering novel alkalides with superalkali clusters: Ab initio insights into nonlinear optical responses

We designed novel alkalides such as FLi2-M-OLi3 and FLi2-M-NLi4 (M = Li, Na, K), along with OLi3-M-NLi4 (M = Li, Na) by interacting alkali metal atoms with heterogeneous superalkali clusters in anionic, neutral and cationic configurations. The stability of these superalkali based alkalides are confirmed by its binding energy (Eb). Utilising QTAIM method, the bond strength and nature of bond have been analysed. NPA charge analysis is conducted to forecast charge transfer and also to confirm the alkalide character of the complex along with the electron localisation function (ELF) analysis. The HOMO–LUMO gap analysis is performed to analyse electrical conductivity and chemical reactivity. The nonlinear optical (NLO) properties have been investigated by polarisability and first-order static hyperpolarizibilty (β0), which is found to be as high as 2.77 × 107 a. u. for (OLi3-Li-NLi4)+ complex. The UV-Vis spectra and electronic transitions are used to explain the enhanced NLO responses. The study not only identifies new alkalide candidates but also presents strategies to significantly improve their NLO properties, which may be useful in nonlinear optics and optoelectronics.