Hyperfine and nuclear quadrupole coupling in chlorine and fluorine dioxides

The hyperfine and nuclear quadrupole coupling tensors have been calculated for the two chlorine dioxide isomers OC10 and C100 and for fluorine dioxide FOO. The coupled-cluster singles and doubles (CCSD) approach with a perturbative treatment of triple excitations [CCSD(T)] has been used and basis saturation has been investigated. For the symmetric isomer OC10 close agreement is obtained with the accurate and detailed experimental data. For FOO a geometry optimization as well as a comparison of calculated and experimental hyperfine coupling tensors suggest a shorter F-O bond length than that obtained experimentally. For the isomer C100, calculations have been carried out at the theoretical equilibrium geometry determined by Peterson and Werner and at the geometry proposed by Byberg for the matrix isolated molecule. The hyperfine coupling tensors obtained at these two geometries are substantially different, but the estimated accuracy of the calculations is not high enough to allow a determination of the geometry of C100 from the hyperfine data. (C) 1997 American Institute of Physics.