Third-order nonlinear optical studies of Bis(4-methylbenzylammonium) tetrachloridocuprate metal-organic crystal with optical limiting behavior: Experimental and theoretical investigations

Abstract

The metal-organic nonlinear optical (NLO) compound Bis(4-methylbenzylammonium) tetrachloridocuprate (4MBA) was synthesized and grown by the slow evaporation method. X-ray crystal analysis revealed the crystal structure and conformation. Density functional theory (DFT) at B3PW91/LanL2DZ basis set level was applied and computed the optimized geometry, electronic structure, vibrational spectra, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), and natural bonding orbitals (NBO). UV–Vis-NIR spectroscopic measurements revealed the optical transparency range from 310 to 1100 nm and excited-state properties. The thermal behavior and stability of the compound were analyzed using TGA/DTA, and the suitability of the optical material is weighed. The dielectric parameters and AC conductivity were investigated as a function of frequency and temperature. Second-harmonic generation (SHG) efficiency was measured using the Kurtz and Perry powder approach and found 4MBA to be 0.8 times the KDP. The nonlinear refractive index (n2), nonlinear optical absorption (β) and third-order nonlinear optical susceptibility (χ(3)) measured values are 1.548 × 10−9 cm2 W−1, 0.0538 × 10−4 cm W−1, and 6.049 × 10−8 esu respectively, and shows that the 4MBA molecule is a third-order nonlinear optical material. The optical limiting threshold value is determined as 7.632 × 103 W cm2 for 532 nm continuous-wave laser, representing that the 4MBA is a strong candidate for the optical limiting application. The static and dynamic nonlinear optical parameters were computed with three different functions including B3PW91, M06 and PBE0 using LanL2DZ basis set. The outcomes revealed that the 4MBA molecule under study might be a promising NLO material for frequency generators and optical limiters applications.