Ab initio MODPOT / VRDDO / MERGE calculations on energetic compounds. III. Nitroexplosives: Polyaminopolynitrobenzenes (including DATB, TATB, and tetryl)

Quantum chemical ab initio MODPOT / VRDDO calculations have been carried out on the following aminonitrobenzenes for which crystal structures had been determined experimentally: 4‐nitroaniline; N,N‐dimethyl‐p‐nitroaniline; 2,4,6‐trinitroaniline; 1,3‐diamino‐2,4,6‐trinitrobenzene (DATB—Form I); 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB); 2,3,4,6‐tetranitroaniline; N‐methyl‐N,2,4,6‐tetranitroaniline (Tetryl); and N‐(β,β,β‐trifluoroethyl)‐N,2,4,6‐tetranitroaniline. These quantum chemical calculations were performed on the molecules in their conformations as found in their crystal structures. The calculations were carried out with our own ab initio programs which also incorporate as options several desirable features for calculations on large molecules: ab initio effective core model potentials (MODPOT) which enable calculations of valence electrons only explicitly, yet accurately, and a charge conserving integral prescreening evaluation (which we named VRDDO‐variable retention of diatomic differential overlap) especially effective for spatially extended molecules. Aminonitrobenzenes are especially interesting since there are inherent intramolecular ring distortions and deviations from planarity and intramolecular hydrogen bonds as well as intermolecular hydrogen bonds causing further deviations from planarity. The theoretical indices resulting from the quantum chemical calculations are relevant to a number of properties and behavioral characteristics of these molecules, both intramolecular and intermolecular. The charges on the atoms [from the gross atomic populations ( GAP 's)] are needed for calculation of the atomic multipole–atomic multipole electrostatic contributions (a dominant factor) to the intermolecular interaction energies. These electrostatic interaction energies are part of the input necessary for calculations on the crystal packing and densities of these molecules. These GAP 's are also of value in interpreting the experimental photoelectron and ESCA spectra of these molecules. The total overlap populations ( TOP 's) between atoms are related to the inherent bond strengths and can serve as a quantitative replacement for the old empirical bond length‐bond order‐bond energy relationship still used by explosives chemists to identify the “target bonds” (the weakest bonds). The TOP 's are of considerable value in predicting and tracing initiation and subsequent steps of explosive phenomena. The molecular orbital energies of the lowest unoccupied orbitals are of interest since nitroexplosives have been implicated in testicular toxicity and the initial metabolic activation appears to proceed through a one‐electron reduction of the nitroexplosive.