Self and hetero-association in Benzaldehyde/Quinoline - Formamide solutions: Time Domain Reflectometry studies

The complex permittivity spectra of binary solutions of Benzaldehyde (PhCHO)/Quinoline (QUI) with Formamide (FMD) have been obtained at different mole fractions of FMD in the frequency range from 10 MHz to 30 GHz using the Time Domain Reflectometry (TDR) technique. The complex permittivity spectra have been fitted with Debye function. Dielectric relaxation time values have been interpreted in terms of the nature and size of the self and hetero associates of the binary solutions. The effective Kirkwood correlation factor (geff) has been correlated with closed and open associates of the solutions. The geff similar to 0.51 is the characteristic value of closed dimers. It appears that geff similar to 0.75 signifies the presence of both closed and open dimers. The Excess static dielectric constant (epsilon E) shows negative deviation. The corrective Kirkwood correlation factor (gf) and Bruggeman factor (fB) have been used to investigate the strength of the H-bond interactions. The Geometry optimization has been carried out using Density Functional Theory (DFT) with B3LYP/6-311++G (d, p) basis set. Population analysis on the optimized geometries shows that PhCHO has 53.61 and 46.39 % closed and open geometries, respectively, while FMD has 17.11 % open dimers and remaining are closed dimers.