DFT study of electronic and nonlinear optical properties of alkaline earth metals and superalkalis doped all-cis-1, 2, 3, 4, 5, 6-hexafluorocyclohexane as an efficient excess electron system

Abstract Continual advancements are being pursued to discover innovative strategies for developing materials with remarkable nonlinear optical (NLO) response. Herein, electronic, geometric, thermodynamic and NLO properties of excess electron systems based on stacked Janus dimer, all- cis -1,2,3,4,5,6-hexafluorocyclohexane (C 6 H 6 F 6 ) 2 are thoroughly investigated. The excess electron systems are designed by doping alkaline earth metals (AEMs) on fluorine face and superalkalis on hydrogen face of Janus dimer. The higher values of vertical ionization energies (VIE) and interaction energies (E int ), confirm the electronic and thermodynamic stabilities of the designed complexes, respectively. Natural bond orbital (NBO) analysis is performed, and the excess electron character of the complexes is confirmed through frontier molecular orbital (FMO) analysis by highest occupied molecular orbital (HOMO) iso-densities. FMO shows a significant decrease in energy gaps (E gap ) of the complexes (i.e., E g = 1.80–3.12 eV), compared to the stacked Janus dimer (i.e., E g = 9.41 eV). The transparency of the complexes to UV region is confirmed through UV–vis analyses, revealing their maximum absorption in visible and near-IR regions. The higher NLO response of the designed excess electron systems is further proved by the greater values of first hyperpolarizability ( β o ) i.e., up to 1.70 × 10 6 au. Moreover, the time dependent-density functional theory (TD-DFT) computations and two-level model are employed to investigate the controlling factors of hyperpolarizability, illustrating the contribution of transition energy (∆E 3 ), change in dipole moment (∆ μ ) and oscillator strength ( f o ) in controlling the β o . Ab-initio molecular dynamics (AIMD) simulation further confirm that the designed superalkalide complexes are kinetically and thermally stable. The thorough investigation of these excess electron systems proves them an appropriate candidate for NLO applications.