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The high-accuracy W4 computational thermochemistry protocol, and several post-W4 methods, have been applied to the P and P molecules. Contrary to previous studies, we find the experimental thermochemistry to be fundamentally sound. The reaction enthalpy for PP 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}\pm\Delta H^\circ_{f,298}\pm$0.1 kcal/mol, in the upper half of the CODATA uncertainty interval.

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