Accurate or Fast Prediction of Solid-State Formation Enthalpies Using Standard Sublimation Enthalpies Derived From Geometrical Fragments

In
view of its success in predicting sublimation enthalpies of
molecular crystals near triple point conditions [Ind. Eng.
Chem. Res. 2012, 51, 2814],
the geometrical fragment (GF) approach is presently used to estimate standard values ΔsubH0 adjusted to the reference temperature of 298.15 K. The resulting
GF0 scheme is fitted against theoretically confirmed ΔsubH0 data for 185 high nitrogen
compounds and validated using organic compounds not used in the fitting
process. It is subsequently used to predict the solid-state formation
enthalpy ΔfH0(cr) of
40 energetic materials, combined with either correlated ab initio
methods or simple models to estimate the gas-phase contribution. The
combination of GF0 with ab initio data yields ΔfH0(cr) values with state-of-the-art
accuracy. Combined with the simple atom pair contribution model, this
procedure predicts ΔfH0(cr) with better accuracy and stronger physical grounds than alternative
low-cost methods.