Theoretical study of the structure and energy performance of nitroformates and mono-, di-, tri- and tetranitromethanes

Using the methods of quantum chemistry and atom-atom potentials, the molecular and crystal structure of a number of nitromethanes and their salts was modeled. Their thermochemical characteristics were assessed. A comparison of the calculated values of the enthalpies of salt formation with experimental data known for some of the presented compounds indicates that the author's method (MICCM), based on modeling the structure of compounds of ionic form and their cocrystals, gives the most accurate values of the enthalpy of salt formation compared to other known calculation methods. As a result of the simulation, the structure was predicted and the enthalpies of previously unstudied salts were determined, as well as new, unknown polymorphic structures of neutral nitromethanes and their salts. Modeling of the crystal structure of nitromethanes and their salts through the prediction of packings and further evaluation of thermochemical properties by the author's method. • New possible polymorphic modifications of nitromethanes were suggested • The anion contribution was found for estimating the enthalpy of formation of salts • The method of mixing salts and cocrystals has received additional confirmation