Preserving the symmetry of cis-1,2-difluoroethylene in the gas-phase heterodimer with hydrogen chloride: A microwave rotational study revealing a novel structure

• Published in: The Journal of chemical physics 2024-09, Vol.161 (10)
• Main Authors: Leung, Helen O., Marshall, Mark D.
• Format: Article
• Language: English
• Subjects: Acetylene; Atomic structure; Chlorine; Electron spin; Equivalence; Fluorine; Fourier transforms; Hydrochloric acid; Hydrogen; Hydrogen atoms; Hydrogen bonds; Hydrogen chloride; Linearity; Microwave spectra; Molecular structure; Nuclear spin; Quantum chemistry; Rotational spectra; Symmetry
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/5.0231236

The microwave spectra of three isotopologues of the gas-phase heterodimer formed between cis-1,2-difluoroethylene and hydrogen chloride are obtained in the 5–21 GHz region using Fourier transform microwave spectroscopy. The molecular structure, determined from the analysis of the spectra and supported by quantum chemistry calculations, has the hydrogen atom of the hydrogen chloride molecule interacting with both fluorine atoms of the fluoroethylene and no interaction between the chlorine atom and the olefin. Although the equilibrium structure has two inequivalent H⋯F interactions, zero-point motion averages over the two equivalent choices for these interactions, rendering the pairs of like atoms (C, H, and F) of the fluoroethylene equivalent, retaining the C2v symmetry of the olefin. This results in only one unique singly substituted 13C isotopologue and in the observed effects on transition intensities due to nuclear spin statistics. The heterodimer structure allows for a strong, linear hydrogen bond between the HCl donor and the fluoroethylene acceptor that is more important here than in the analogous acetylene containing complex, where the interaction between the π electrons of acetylene and an electrophilic hydrogen atom on the olefin compensates for the loss of linearity required for binding to a geminal F/H pair.