Atom Pair Contribution Method: Fast and General Procedure To Predict Molecular Formation Enthalpies

An atom pair contribution (APC) model aimed at predicting the gas-phase formation enthalpy (ΔfH°) of molecules is reported. In contrast to bond contribution (BC) or group contribution (GC) methods, it relies on increments associated with pairs of bonded and geminal atoms along with 15 structural corrections. Another distinctive feature of the present APC method is the large amount of experimental and high-level theoretical data specially compiled in this work to fit and validate the model (2671 entries). Unlike GC methods, the present APC model has wide applicability with the number of adjustable parameters limited to 68. Although it requires only a structural formula as input and involves only back-of-the-envelope calculations, it is more reliable than state-of-the-art quantitative structure–property relationship methods, popular semiempirical Hamiltonians, and even low-level density functional theory approaches based on gradient-corrected functionals. It is therefore a valuable tool for fast screening applications or whenever chemical accuracy is not necessary.