A Quantum Chemical Study on the Enormously Large Nonlinear Optical Response of Doped Endohedral Superalkali Na 2 F and Superhalogens MF 4 (M = B, Al) with CNT (C56H16) Cage

In the present communication, the interaction of single‐wall carbon nanotubes (SWCNTs) CNT (C56H16) with endohedral doped superhalogens (MF 4 :M = B, Al) placed outside of CNT cage and superalkali (Na 2 F) placed inside the cage has been studied by using a combination of DFT/B3LYP method and 6–311G(d, p) basis set. The geometry and stability of MF 4 @CNT‐Li 2 F have been studied using optimization parameters, highest occupied molecular orbit (HOMO), lowest unoccupied molecular orbital (LUMO), vibration frequencies, and thermodynamic parameters of absorption reactions. The quantum theory in atoms in molecules (QTAIM) analysis is used to analyze the nature of interactions between MF 4 (M = B, Al) and Na 2 F@CNT. Several electronic parameters are computed by using HOMO–LUMO energy. The dipole moment, polarizability, hyperpolarizability, order parameters, anisotropic polarizability, and molar refractivity of MF4@CNT‐Li 2 F (M = Al, B) are used to calculate the nonlinear optical parameters (MR). The NBO analysis is used to calculate the transfer of charge to stabilized system. The calculated hyperpolarizability of Na 2 F@CNT‐BF 4 /Na 2 F@CNT‐AlF 4 is nearly 81 times that of reference material urea (40 a.u.). The intramolecular charge transfer (ICT) moment of π electron cloud is responsible for the nonlinear optical behavior of the system.