title: C-H bonds with a positive dipole gradient can form blue-shifting hydrogen bonds: the complex of halothane with methyl fluoride.
abstract: The complex of halothane (CF(3)CBrClH) with ([D(3)])methyl fluoride is investigated theoretically by means of ab initio calculations at the MP2/6-311++G(d,p) level and experimentally by infrared spectroscopy of solutions in liquid krypton. The complexation energy is calculated to be -12.5 kJ mol(-1). The dipole moment of halothane monomer as a function of the C-H stretching coordinate is calculated with different methodologies and the value of (partial differential(mu)/partial differential(Q(1)))0 is found to be positive. In the spectra, formation of a 1:1 complex is observed. The standard complexation enthalpy is measured to be -8.4(2) kJ mol(-1). The C-H stretching vibration of halothane shows a blueshift of +15.4 cm(-1) on complexation, and its infrared intensity ratio epsilon(complex)/epsilon(monomer) is found to be 1.39(7). The frequency shift is analyzed by a Morokuma analysis, and the infrared intensities are rationalized by using a model which includes the mechanical and electrical anharmonicity of the C-H stretching vibration.
authors.affiliation: Department of Chemistry, University of Antwerp, Groenenborgerlaan 171, B2020 Antwerp, Belgium.
authors.forename: Bart
authors.initials: B
authors.lastname: Michielsen
authors.forename: Wouter A
authors.initials: WA
authors.lastname: Herrebout
authors.forename: Benjamin J
authors.initials: BJ
authors.lastname: van der Veken