W4 thermochemistry of P₂ and P₄. Is the CODATA heat of formation of phosphorus atom correct?

The high-accuracy W4 computational thermochemistry protocol, and several post-W4 methods, have been applied to the P$_2$ and P$_4$ molecules. Contrary to previous studies, we find the experimental thermochemistry to be fundamentally sound. The reaction enthalpy for P$_4\to 2$P$_2$ has a very significant contribution from post-CCSD(T) correlation effects. We derive a gas-phase heat of formation for the phosphorus atom of $\Delta H^\circ_{f,0}$[P(g)]=75.54$\pm$0.1 kcal/mol and $\Delta H^\circ_{f,298}$[P(g)]=75.74$\pm$0.1 kcal/mol, in the upper half of the CODATA uncertainty interval.