Vibrational spectroscopy of dynamic interactions and relaxation processes in ionic systems.

In recent years, there has been a boom in the publication of research results on ionic (electrolyte) systems used in the creation of electrochemical energy systems (batteries, supercapacitors, etc.). One of the alternative ways to obtain dynamic information in ionic systems is spectroscopic experiments, and the most valuable information on the behavior of condensed systems at picosecond and adjacent time intervals is provided by vibrational spectroscopy. The source of this information is the analysis of the shape and width of the lines in the vibrational spectra of ion systems. This review aims to systematize the theoretical and methodological aspects of the study of the dynamics of ion systems by vibrational spectroscopy.

Lignin-Based Gel Polymer Electrolyte for Cationic Conductivity.

The article presents the results of the preparation and study of a gel-polymer electrolyte based on lignin obtained from Pinus sylvestris. Sulfonation and subsequent chlorination of lignin make possible implementation of the principle of mono-ionic conductivity in a natural biopolymer matrix, which provides predominantly cationic conductivity of the electrolyte. Based on the results of the qualitative and quantitative analysis of the synthesized samples, the mechanisms of the chemical conversion of the biopolymer, the structure models of the converted fragments of macromolecules, as well as the quantum-chemical calculation of their electronic and geometric parameters are presented. The key electronic characteristics of the gel polymer electrolytes (GPE) based on a composite of lignins with 20 wt.% polyvinyl alcohol are determined by impedance spectroscopy. The maximum value of the specific volume conductivity is 2.48 × 10-4 S cm-1, which is comparable with most commercial electrolytes of this type, but at the same time, record values are reached in the number of lithium cation transfer tLi+ of 0.89. The studies allow to identify the basic laws of the effect of chemical modification on the structure of GPE and describe the mechanism of ionic conductivity.

Self-association and picosecond dynamics in liquid dimethyl sulfoxide.

Dimethyl sulfoxide (DMSO) has been known for almost 150 years, but its properties as a solvent and reaction medium are far from being understood. In particular, association equilibriums in liquid DMSO have been characterized in just four papers, and the enthalpy of its self-association is unknown. The aims of this paper are to study self-association equilibriums in neat liquid DMSO at various temperatures by means of Raman spectroscopy, to find the enthalpy of self-association, and to solve the problem of hydrogen bonding in this liquid. Time correlation functions of vibrational dephasing and reorientation of coexisting monomers and dimers studied by the C-S-C and C-H symmetric vibrations indicate that external perturbations and vibrational and reorientational dynamics of these particles occur on different time scales. No signatures of H-bonding in DMSO are found. The association constants vary from 0.20 L mol(-1) (23 °C) to 0.081 L mol(-1) (100 °C). Their temperature dependence gives the enthalpy of association of DMSO as -11.7 ± 0.9 kJ mol(-1).