Structure, Conformational Equilibria, and Weak Hydrogen Bonding in the CH2 F2 -CF3 CH2 F Dimer

Abstract

To probe the multiple configurations of a weakly bound intermolecular complex, the difluoromethane and 1,1,1,2-tetrafluoroethane dimer was investigated by using pulsed jet Fourier transform microwave spectroscopy coupled with quantum chemical calculations. Three isomers were detected in the supersonic jet. Spectroscopic assignments, ab initio calculations and quantum theory of atoms in molecules (QTAIM) analyses prove that all the observed isomers are stabilized through a net of three weak C-H⋅⋅⋅F-C interactions. The interaction energies are estimated to be within 12-13 kJ mol^-1 , dominated by electrostatic and dispersion according to Symmetry-Adapted Perturbation Theory (SAPT) analysis. The spectroscopic measurements were also extended to three and two ¹³ C isotopologues in natural abundance for the isomers II and III, respectively, which lead to precisely structural determinations of these two isomers. The comparison of the relative intensity of these isomers measured in the carrier gases of argon and helium evidenced that isomer II is the global minimum, while the intensities measured in helium suggested that the population of the three isomers in the jet to be N_I /N_II /N_III ≈1/11/4.

Keywords: conformational equilibria; halocarbons; hydrogen bonds; non-covalent interactions; rotational spectroscopy.