Ab initio reaction dynamics of the unimolecular dissociation of tert-butyl iodide at room temperature were investigated using large high-performance computing clusters running in parallel. The potential energy surface calculations were performed in different solvent environments that included acetone, acetonitrile, carbon tetrachloride, chloroform, dichloromethane, dimethylformamide, dimethyl sulfoxide, ethanol, hexane, methanol, pyridine, tetrahydrofuran, toluene, and water. Starting with an optimized molecular geometry of tert-butyl iodide in the different solvents above using a Karlsruhe valence triple-zeta polarization as a basis set of functions for the calculations, the C-I bond dissociation energies were derived following relaxed potential energy surface scans associated with a series of 0.05 Å C-I bond length increases that ultimately broke the carbon-iodine bond. Dissociation energy results, as ratios and differences in the fourteen solvents, were plotted side by side with solvent types, polarity strengths, Reichardt and Snyder polarity indices, refractive indices, and dielectric constant (ε) values to reveal trends. The dissociation energy results were subsequently plotted against a subset of relevant solvent properties from the list above to elucidate relationships.

Ab initio investigation of the solvent-facilitated unimolecular dissociation dynamics of the tert-butyl iodide potential energy surface using high-performance parallel computing

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.