J Phys Chem A. 2022 Jul 29. doi: 10.1021/acs.jpca.2c01114. Online ahead of print.
A new efficient method for calculating the enthalpies of salt formation is proposed. The method is based on a fundamentally new cocrystal model, consisting of a mixture of cations and anions and a “quasi-salt” of neutral components, in fact, of the salt itself, and the enthalpy of formation is calculated as the average value between the enthalpies of formation of these two structural components. Unlike correlation and additive schemes, this method is based on the construction of a real physical model of a salt crystal, for which the molecular geometry of the ions and neutral salt components is preliminarily optimized by quantum chemistry methods. Further, based on the obtained data, the initial models of crystal lattices in the statistically most probable structural classes are constructed with their subsequent optimization by the method of Atom-Atom potentials. For a number of compounds of various chemical classes, the effectiveness of the method for estimating the enthalpy of salts is shown, which surpasses the known methods in terms of calculation accuracy.