Theoretical Studies on Ion Solvation in Non-Aqueous Solvents.
ARMY ELECTRONICS COMMAND FORT MONMOUTH N J
Pagination or Media Count:
Molecular orbital calculations are used to study the nature of ion solvation and solvent structure. Comparing sulfur dioxide SO2 and tetrahydrothiophene THT additions to propionitrile and propylene carbonate, it is found that in SO2 containing solvents, Cl- ion solvation is stabilized by coordination to the sulfur by considerable charge transfer to both the S and O atoms. In the THT-Cl- complex, charge transfer is not as complete and the S-Cl sigma-bond contains a much larger s-orbital contribution thereby resulting in a much weaker bond. Semiempirical molecular orbital calculations are also reported for methanol chains of up to 6 molecules in length. The theoretical data are in agreement with various experimental spectroscopic and dielectric relaxation data and a mechanism of dipole relaxation based on a dipole-field assisted rotation is suggested. Molecular orbital calculations are reported for ion-solvation in methanol and compared with water solvation.
- Atomic and Molecular Physics and Spectroscopy