Tuning nonlinear optical properties of tetracyclopentatetraphenylnene by superhalogens doping: Quantum chemical perspective of novel NLO materials for modern optoelectronic applications

Fabrication of stable NLO materials is highly demanding because of their numerous applications in optoelectronic and optical devices. This research attempts to theoretically design superhalogens (LiF₂, BeF₃, MgF₃, LiCl₂, BeCl₃, MgCl₃) doped tetracyclopentatetraphenylnene (TCPTP) as potential NLO materials for cutting-edge NLO applications. Density functional theory (DFT) computations explore their geometric, thermodynamic, electrical, and nonlinear optical (NLO) properties. NCI analysis, DOS, FMO, MEP, TDM, and NBO analysis are performed to confirm the type of interaction, participation of various fragments, and charge transfer, respectively. The computational findings demonstrated that the superhalogen-doped isomers of TCPTP have remarkable thermodynamic stabilities, with the highest binding energy of −81.344 kcalmol⁻¹. The HOMO–LUMO energy gap was significantly decreased from 1.5319 eV (TCPTP) to 1.2807––1.2269 eV by superhalogens doping. The TD-DFT analysis demonstrates that these proposed complexes have sufficient transparency in the UV region, which is necessary to add a high nonlinear optical response for valuable applications in optoelectronics. Magnification in the dipole moment (µ₀), polarizability (α₀), and hyperpolarizability (β₀) values from 0.0 D, 325.00 a.u. and 0.0 a.u to 18.23 D, 463.92 a.u and 4.11 × 10⁴ a.u respectively, is achieved upon superhalogens doping on TCPTP surface. These complexes also had considerably large initial hyperpolarizability (βo) from 1.57 × 10³ to 4.11 × 10⁴ au, which was particularly noteworthy. This research with promising initial hyperpolarizability (β_o) value will provide new opportunities for experimental and theoretical researchers to develop innovative NLO materials.