Ab initio calculations of the effective spin-spin parameter λ, and of electric dipole intensities for the forbidden 1Σ+-3Σ- transition, are reported for NH, NF, PH, PF, NCl and SO, and values of λ alone are calculated for O2 and S2. In general the values of λ agree to within 10 per cent with the experimental values, and the calculations enable the apparently irregular variation of λ within this class of molecules to be explained. The effect on λ of several approximations has been investigated, and it is found that the simplest model considered gives reasonable agreement with experiment, as others have found in comparable cases. This model employs single configuration wavefunctions in which the 3Σ- orbitals are used to represent the isoconfigurational 1Σ+ state; only the interaction with this one 1Σ+ state is included, and only one-centre spin-orbit integrals are retained. Values of λ were calculated at three internuclear separations bracketing the experimental equilibrium separation, so that the vibration...