ABSTRACT
The molecular structure and infrared spectrum of the atmospheric pollutant 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243) were characterized experimentally and theoretically. The theoretical calculations show the existence of two conformers, with the gauche (G) and trans (T) orientation around the HCCC dihedral angle. Conformer G was calculated to be more stable than form T by more than 10 kJ mol (-1). In consonance with the large predicted relative energy of conformer T, only the G form was identified spectroscopically in cryogenic argon (10 K) and xenon (20 K) matrices prepared from room-temperature equilibrium vapor of the compound. The observed infrared spectra of the matrix-isolated HCFC-243 were interpreted with the aid of high-level density functional theory calculations and normal coordinate analysis. For experimental identification of the weakest IR absorption bands, the spectrum of HCFC-243 in the neat solid state at 145 K was obtained. This spectrum also confirmed the sole presence of the G conformer in the sample. Natural bond orbital and atomic charge analyses were carried out for the two conformers to shed light on the most important intramolecular interactions in the two conformers, in particular those responsible for their relative stability.
ABSTRACT
The optimised geometries of heterocyclic hydrogen-bonded complexes, C2H4O...HX and C3H6O...HX, where X=F or Cl, were determined at DFT/B3LYP/6-311++G(d,p) computational level. Structural, electronic and vibrational properties of these complexes are used in order to compare the strained ring, which confer the great reactivity of these heterocyclic rings with monoprotic acids, forming a primary hydrogen bond. A secondary hydrogen bond between the hydrogen atoms of the CH2 groups and the halide species also takes place, thus causing a nonlinearity (characterized by the theta angle), in the primary hydrogen bond.
