Novel endohedrally and exohedrally metals (Li, Na, and K, Ag) doped (15-crown-5) with remarkable electronic, static and dynamic NLO response

In this study, an intriguing class of new complexes, in which 15-crown-5 is encapsulated by the Ag metal and exohedrally doped with alkali metals (Li, Na and K) is being explored for its electronic and optical response using ωB97XD/LANL2DZ functional of DFT. The three new complexes are thermally stable as evident from their interaction energy calculations. The alkali metals render excess electrons to the system which significantly reduced the HOMO-LUMO gap of new systems as compared to the bare crown. The intramolecular interactions are being evaluated by NBO analysis which revealed the alkali metals as donor species and Ag metal as an accepting moiety. The transparency of complexes in deep-UV region and monotonically decreasing excitation energy are key factors in proving their utility in optoelectronics. The estimation of static and dynamic first and second order hyperpolarizabilities reveal the significantly pronounced results. The maximum static first and second order nonlinearity are calculated for Ag(CR)K which are β0 = 3.69 × 104 au and γ0 = 5.08 × 105 au, respectively. The exceptionally high dynamic second hyperpolarizability for electric-field induced SHG is estimated to be 1.31 × 1010 au. The overall detailed study proves these materials as powerful candidates for NLO materials.