Molecular Structures and Microwave Spectra of the Gas-Phase Homodimers of 3-Fluoro-1,2-epoxypropane and 3,3-Difluoro-1,2-epoxypropane.

Abstract

Molecular structures for the heterochiral and homochiral gas-phase homodimers of 3-fluoro-1,2-epoxypropane and 3,3-difluoro-1,2-epoxypropane are investigated using both ab initio and density functional quantum chemistry calculations. Although microwave spectra for the heterochiral dimers are not observed as the lowest-energy isomers lack an electric dipole moment and others are presumably too high in energy, rotational spectra are observed for the homochiral dimers of each molecule that are consistent with the lowest-energy isomers of each. The presence of hydrogen atoms in the fluoromethyl groups makes it possible for these groups to participate in the intermolecular interactions that stabilize these dimers, resulting in a distinctly different bonding motif than is observed in the homodimers of 3,3,3-trifluoro-1,2-epoxypropane where the lack of a hydrogen atom prevents this possibility. The rotational spectra and energy ordering of the dimers are sufficiently well predicted with modest calculational methods to enable straightforward assignment of the observed spectra and to identify the molecular carrier of an assigned spectrum.