In an attempt to extend the applicability of the W1 and W2 ab initio computational thermochemistry methods, we propose explicitly correlated versions thereof, denoted W1-F12 and W2-F12. In W2-F12, we can “save” one cardinal number (viz., angular momentum) in the basis set sequences without loss in accuracy; in W1-F12, we can do so for first-row compounds but not for second-row compounds. At a root mean square deviation (RMSD) = 0.19 kcal/mol for the first-row molecules in the W4-11 benchmark dataset, W1-F12 is in fact superior to ordinary W1 theory. For the entire W4-11 set, W2-F12 yields a RMSD = 0.20 kcal/mol, comparable to 0.19 kcal/mol from ordinary W2 theory. The extended applicability ranges of W1-F12 and W2-F12 are not just due to the lower computational cost but also to greatly reduced memory and especially storage requirements. They are illustrated through applications to nucleic acids and to polyacenes (with up to four rings), for which the following revised gas-phase heats of formation are found: $\Delta _fH^\circ _{298}$ = 19.6 (benzene), 34.94 (naphthalene), 53.9, (anthracene), 73.9 (naphthacene/tetracene), 54.9 (adenine), −16.3 (cytosine), 5.1 (guanine), −80.6 (thymine), and −71.6 (uracil) kcal/mol. Our theoretical values for the DNA/RNA bases largely confirm recent predictions based on much lower-level calculations. The W1-F12 theoretical values for benzene, naphthalene, and anthracene are in very good to reasonable agreement with experiment. However, both W1-F12 and other computational estimates show that the accepted experimental value for naphthacene cannot be reconciled with those for the lower acenes: we suggest that $\Delta _f H^\circ _{298}$[naphthacene(g)] = 74.25 ± 1 kcal/mol is a more realistic estimate.
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