Heats of formation of perchloric acid, HClO4, and perchloric anhydride, Cl2O7. Probing the limits of W1 and W2 theory

The heats of formation of HClO4 and Cl2O7 have been determined to chemical accuracy for the first time by means of W1 and W2 theory. These molecules exhibit particularly severe degrees of inner polarization, and as such obtaining a basis-set limit SCF component to the total atomization energy becomes a challenge. (Adding high-exponent d functions to a standard spd basis set has an effect on the order of 100 kcal/mol for Cl2O7.) Wilson’s aug-cc-pV(n+d)Z basis sets represent a dramatic improvement over the standard aug-cc-pVnZ basis sets, while the aug-cc-pVnZ+2d1f sequence converges still more rapidly. Jensen’s polarization consistent basis sets still require additional high-exponent d functions: for smooth convergence we suggest the {aug-pc1+3d,aug-pc2+2d,aug-pc3+d,aug-pc4} sequence. The role of the tight d functions is shown to be an improved description of the Cl (3d) Rydberg orbital, enhancing its ability to receive back-bonding from the oxygen lone pairs. In problematic cases like this (or indeed in general), a single SCF/aug-cc-pV6Z+2d1f calculation may be preferable over empirically motivated extrapolations. Our best estimate heats of formation are ∆H◦ f,298[HClO4(g)] = −0.6±1 kcal/mol and ∆H◦ f,298[Cl2O7(g)] = 65.9±2 kcal/mol, the largest source of uncertainty being our inability to account for post-CCSD(T) correlation effects. While G2 and G3 theory have fairly large errors, G3X theory reproduces both values to within 2 kcal/mol. ∗Electronic address: [email protected]