Accurate D0 values for SiF and SiF+

Highly accurate D0 values are determined for SiF and SiF+ using the CCSD(T) approach in conjunction with basis set extrapolation. The results include the effect of spin–orbit coupling and core–valence correlation. Our best D0 estimates for SiF and SiF+ are 141.5 and 159.7 kcal/mol, respectively, which we estimate to have an uncertainty of ±1.0 kcal/mol. For SiF, the value is significantly larger than the older experiments and only slightly larger than the most recent experiment. Our value is slightly larger than previous calculations. For SiF+ our best estimate is in good agreement with previous calculations and slightly smaller than the experimental value.