Theoretical calculations of solvation ۱۲-Crown-۴ (۱۲CN۴) in aqueous solution and its experimental interaction with nano CuSO۴

Theoretical study of the electronic structure, and nonlinear optical properties (NLO) analysis of ۱۲-crown-۴were done using Density Functional Theory (DFT) evaluations at the B۳LYP/۶-۳۱۱G (d,p) level of theory. The optimized structure is nonlinear compound as indicated from the dihedral angles were presented. The calculated EHOMO and ELUMO energies of ۱۲-Crown-۴ (۱۲CN۴) can be used to explain the charge transfer in ۱۲-Crown-۴ (۱۲CN۴) and to calculated the global properties; the chemical hardness (η), softness (S) and electronegativity (χ). The NLO parameters: static dipole moment (µ), polarizability (α), anisotropy polarizability (Δα) and first order hyperpolarizability (βtot) of the ۱۲-Crown-۴ (۱۲CN۴) have been calculated at the same level of theory.The molecular electrostatic potential (MEP) and electrostatic potential (ESP) for the title molecule were investigated and analyzed.  Also the electronic absorption spectra were measured in ethanol and water solvents and the assignment of the observed bands has been discussed by time-dependent density functional theory (TD-DFT) calculations. The correspondences between calculated and experimental transitions energies are satisfactory. From the experimental conductance measurements, the association thermodynamic parameters (KA, ∆GA, ∆HA and ∆SA) and complex formation thermodynamic parameters (Kf, ∆Gf, ∆Hf and ∆Sf) for nano-CuSO۴ in presence of ۱۲-crown-۴ (۱۲CN۴) as chelating agent in ۱۰% ethanol – water solvents at different temperatures (۲۹۸.۱۵, ۳۰۳.۱۵, ۳۰۸.۱۵ and ۳۱۳.۱۵K) were applied and calculated.

Keywords:

association parameters , DFT/TD-DFT , formation parameters , nano-CuSO۴ , NLO analysis , UV-spectra , ۱۲-Crown-۴