W4 thermochemistry of P_2 and P_4. Is the CODATA heat of formation of phosphorus atom correct?

Abstract

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 $\Delta H_{f,0}^{\circ }$[P(g)]=75.54$\pm$0.1 kcal/mol and $\Delta H_{f,298}^{\circ }$[P(g)]=75.74$\pm$0.1 kcal/mol, in the upper half of the CODATA uncertainty interval.

arXiv commentMol. Phys., in press (Peter Pulay issue)

References in corpus (2)

• W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions
• Comment on: "Estimating the Hartree-Fock limit from finite basis set calculations" [Jensen F (2005) Theor Chem Acc 113:267]

Cited by in corpus (2)

• Many-body quantum Monte Carlo study of 2D materials: cohesion and band gap in single-layer phosphorene
• MP2-F12 basis set convergence near the complete basis set limit: are $h$ functions sufficient?