Microwave spectra of O2-HF and O2-DF:: Hyperfine interactions and global fitting with infrared data

Spectra of the open shell complexes O-2-HF and O-2-DF were recorded using Fourier transform microwave spectroscopy. A complete analysis of the hyperfine structure and a global fit including microwave and infrared frequencies [W. M. Fawzy, C. M. Lovejoy, D. J. Nesbitt, and J. T. Hougen, J. Chem. Phys. 117, 693 (2002)] are reported. The Fermi contact interaction between the electron and nuclear spins, the electron spin-nuclear spin dipolar interaction, the nuclear spin-nuclear spin dipolar interaction, and the nuclear electric quadrupole interaction (for O-2-DF) were considered in the analysis. The correspondence between the magnetic hyperfine constants and the two nuclei of the H(D)F is unambiguously established. In both O-2-HF and O-2-DF, the Fermi contact parameter is larger for the fluorine than for the hydrogen, while for the nuclear spin-electron spin dipolar hyperfine constants, the reverse is true. The effective angle between the HF bond and the a axis of the complex, determined from the nuclear spin-nuclear spin interaction constant, is 38(4)degrees. The same angle for the DF complex, derived from the deuterium nuclear quadrupole coupling constant, is 31(4)degrees. (c) 2007 American Institute of Physics.