Reliability of Poisson-Nernst-Planck Anomalous Models for Impedance Spectroscopy.

We investigate possible connections between two different implementations of the Poisson-Nernst-Planck (PNP) anomalous models used to analyze the electrical response of electrolytic cells. One of them is built in the framework of the fractional calculus and considers integro-differential boundary conditions also formulated by using fractional derivatives; the other one is an extension of the standard PNP model presented by Barsoukov and Macdonald, which can also be related to equivalent circuits containing constant phase elements (CPEs). Both extensions may be related to an anomalous diffusion with subdiffusive characteristics through the electrical conductivity and are able to describe the experimental data presented here. Furthermore, we apply the Bayesian inversion method to extract the parameter of interest in the analytical formulas of impedance. To resolve the corresponding inverse problem, we use the delayed-rejection adaptive-Metropolis algorithm (DRAM) in the context of Markov-chain Monte Carlo (MCMC) algorithms to find the posterior distributions of the parameter and the corresponding confidence intervals.

Structural investigation of a new cadmium coordination compound prepared by sonochemical process: Crystal structure, Hirshfeld surface, thermal, TD-DFT and NBO analyses.

A new nanostructured cadmium complex containing a tridentate Schiff base ligand was sonochemically synthesized and characterized by XRPD, FT/IR, NMR, and single crystal X-ray crystallography. Structural data showed that cadmium(II) ion is surrounded by three nitrogen atoms of Schiff base ligand and two iodide anions. The crystal packing was contained the intermolecular interactions such as CH⋯O, CH⋯I and π⋯π interactions organizing the self-assembly process. Hirshfeld surfaces and corresponding fingerprint plots have been used for investigation of the nature and proportion of interactions in the crystal packing. FT/IR, NMR and XRD data were in agreement with the X-ray structure and confirm the phase purity of the prepared sample. The molecular structure of the complex was optimized by density functional theory (DFT) calculation at the B3LYP/LANL2DZ level of theory and the results were compared with experimental ones. For more concise study of structure and spectral aspects of the complex, natural bond orbital (NBO) analysis and time-dependent density functional theory (TD-DFT) have been also performed. Thermal stability of the cadmium iodide complex was investigated by thermogravimetric analysis (TGA). Finally, cadmium oxide nanoparticles was prepared by direct calcination of CdLI2 complex as a new precursor.

New tetrahedral zinc halide Schiff base complexes: Synthesis, crystal structure, theoretical, 3D Hirshfeld surface analyses, antimicrobial and thermal studies.

A new bidentate Schiff base ligand named as N,N'-bis((E)-3-phenylallylidene)butane-1,4-diamine (L) and three its zinc halide complexes were synthesized and characterized by FT-IR, 1H NMR, 13C NMR and UV-Vis spectroscopy. The crystal structure of zinc bromide and iodide complexes were characterized using single crystal X-ray diffraction. The two structures are isomorphous, crystallizing in the monoclinic crystal system with space group C2/c with closely similar unit cell dimensions. In these complexes, the Zn(II) ion is in the center of a distorted tetrahedral environment completed by two iminic nitrogen atoms of Schiff base ligand and two halide anions. The analysis of crystal structures shows that intermolecular interactions such as CH⋯halogen, π⋯π and CH⋯π interactions have effective role in stabilization of complexes structure. Intermolecular interactions were more analyzed using 3D Hirshfeld surface analysis and corresponding 2D fingerprint plots. Furthermore, structural optimization by DFT calculations at the B3LYP/LANL2DZ level have been performed and then compared with the experimental data. Time-dependent density functional theory (TDDFT) has been also used to calculate the electronic transitions of molecules at B3LYP/LANL2DZ level using the optimized ground-state geometries. NBO analysis was applied for investigation of intra and inter-molecular bonding and conjugative interaction in molecular systems. Schiff base ligand and their zinc complexes have been screened for their antibacterial and antifungal activities by disc diffusion method. Thermal behaviors of all compounds were studied by TG/DTG analysis data. Also, nanostructures of zinc complexes were synthesized by sonochemical method and characterized by FT-IR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). ZnO nanoparticles were simply prepared by calcination of zinc iodide complex as new precursor at 600°C.