Bond Dissociation Energies of the Tungsten Fluorides and Their Singly Charged Ions: A Density Functional Survey

The dissociation of WF6 and the related singly charged cations and anions into the lower fluorides and fluorine atoms has been investigated theoretically using density functional theory (B3LYP) and relativistic effective core potentials, with estimates of spin−orbit effects included using a simple model. The inclusion of spin−orbit effects is essential for a correct description of the thermochemistry. The total atomization energy of the neutral and anionic WF6 is reproduced to within 25 kcal/mol, but comparison of individual bond dissociation energies with available experimental data shows discrepancies of up to 10 kcal/mol. The results are nevertheless useful to help resolve discrepancies in experimental data and provide estimates of missing data.