Pre-reactive complexes in mixtures of water vapour with halogens: characterisation of H2O...ClF and H2O...F2 by a combination of rotational spectroscopy and ab initio calculations.

Complexes H2O...ClF and H2O...F2 were detected by means of their ground-state rotational spectra in mixtures of water vapour with chlorine monofluoride and difluorine, respectively. A fast-mixing nozzle was used in conjunction with a pulsed-jet, Fourier-transform microwave spectrometer to preclude the vigorous chemical reaction that these dihalogen species undergo with water. The ground-state spectra of seven isotopomers (H2 16O...35ClF, H2 16O...ClF, H2 18O...35ClF, D2 16O... 35ClF, D2 16O...37ClF, HDO...35ClF and HDO...37ClF) of the ClF complex and five isotopomers (H2O...F2, H2 18O...F2, D2O...F2, D2 18O...Fi and HDO...F2) of the F2 complex were analysed to yield rotational constants, quartic centrifugal distortion constants and nuclear hyperfine coupling constants. These spectroscopic constants were interpreted with the aid of simple models of the complexes to give effective geometries and intermolecular stretching force constants. Isotopic substitution showed that in each complex the H2O molecule acts as the electron donor and either CIF or F2 acts as the electron acceptor, with nuclei in the order H2O...ClF or H2O...F2. For H2O...ClF, the angle phi between the bisector of the HOH angle and the O...Cl internuclear line has the value 58.9(16)degrees, while the distance r(O...Cl)= 2.6081(23) A. The corresponding quantities for H2O...F2 are phi = 48.5(21)degrees and r(O...Fi) = 2.7480(27) A, where Fi indicates the inner F atom. The potential energy V(phi) as a function of the angle phi was obtained from ab initio calculations at the aug-cc-pVDZ/MP2 level of theory for each complex by carrying out geometry optimisations at fixed values of phi in the range +/-80degrees. The global minimum corresponded to a complex of Cs symmetry with a pyramidal configuration at O in each. The function V(phi) was of the double-minimum type in each case with equilibrium values phie = +/-55.8degrees and +/-40.5degrees for H2O...ClF and H2O...F2, respectively. The barrier at the planar C2v conformation was V0= 174cm(-1) for H2O...ClF and 7cm(-1) for H2O...F2. For the latter complex, the zero-point energy level lies above the top of the barrier.