Toward subchemical accuracy in computational thermochemistry: Focal point analysis of the heat of formation of NCO and [H,N,C,O] isomers

Abstract

In continuing pursuit of thermochemical accuracy to the level of 0.1 kcal mol−1, the heats of formation of NCO, HNCO, HOCN, HCNO, and HONC have been rigorously determined using state-of-the-art ab initio electronic structure theory, including conventional coupled cluster methods [coupled cluster singles and doubles (CCSD), CCSD with perturbative triples (CCSD(T)), and full coupled cluster through triple excitations (CCSDT)] with large basis sets, conjoined in cases with explicitly correlated MP2-R12/A computations. Limits of valence and all-electron correlation energies were extrapolated via focal point analysis using correlation consistent basis sets of the form cc-pVXZ (X=2–6) and cc-pCVXZ (X=2–5), respectively. In order to reach subchemical accuracy targets, core correlation, spin-orbit coupling, special relativity, the diagonal Born–Oppenheimer correction, and anharmonicity in zero-point vibrational energies were accounted for. Various coupled cluster schemes for partially including connected quadruple excitations were also explored, although none of these approaches gave reliable improvements over CCSDT theory. Based on numerous, independent thermochemical paths, each designed to balance residual ab initio errors, our final proposals are ΔHf,0∘(NCO)=+30.5, ΔHf,0∘(HNCO)=−27.6, ΔHf,0∘(HOCN)=−3.1, ΔHf,0∘(HCNO)=+40.9, and ΔHf,0∘(HONC)=+56.3 kcal mol−1. The internal consistency and convergence behavior of the data suggests accuracies of ±0.2 kcal mol−1 in these predictions, except perhaps in the HCNO case. However, the possibility of somewhat larger systematic errors cannot be excluded, and the need for CCSDTQ [full coupled cluster through quadruple excitations] computations to eliminate remaining uncertainties is apparent.