Experimental and Quantum Chemical Investigation on Piperazinium Hexachloro Stannous Trihydrate Single Crystal for Second Harmonic Generation Applications

Abstract

A metal–organic single crystal of piperazinium hexachloro stannous trihydrate properties are explored through a combined form of experimental and density functional theory. The single crystal of piperazinium hexachloro stannous trihydrate was grown by a solvent evaporation method. All the theoretical calculations have been carried out using a hybrid basis set, B3LYP/6-31G(d,p)/LANL2DZ, with effective core potential. The structural and lattice parameters are confirmed from x-ray diffraction analysis. The functional group vibrational assignments have been theoretically calculated and are well correlated with experimental spectra. Optical studies revealed that the material has 60% transmission in the entire visible region, and a lower cut-off wavelength of about 271 nm where the possible electronic transition is n–σ*. The initial thermal decomposition is started at 60°C, and further decomposition stages have been investigated by thermal analysis. The intermolecular charge transfer, the HOMO–LUMO energy gap and chemical reactivity descriptors are calculated from the frontier molecular orbital analysis. The H···Cl/Cl···H (60%) intermolecular hydrogen bond interactions have the predominant role in determining molecular properties and crystal packing arrangements. The distinct atom-to-atom intermolecular interactions are interpreted through fingerprint plots. The second harmonic efficiency of a titled crystal is 1.8 times greater than that of typical KDP material. The dipole moment, polarizability and first-order hyperpolarizability are 23.89 D, − 2.29 × 10−23 esu and 3.26 × 10−30 esu, respectively, have been calculated from density functional theory. The obtained results show that a piperazinium hexachloro stannous trihydrate crystal could be accepted as a good candidate for nonlinear optical applications.