Molecular Modeling of Energetic Materials:  The Parameterization and Validation of Nitrate Esters in the COMPASS Force Field

To investigate the mechanical and other condensed phase properties of energetic materials using atomistic simulation techniques, the COMPASS force field has been expanded to include high-energy nitro functional groups. In this paper, the parameterization and validation of COMPASS for nitrate esters (−ONO2) is presented. The functional forms of this force field are of the consistent force field type. The parameters were derived with an emphasis on the nonbonded parameters, which include a Lennard-Jones 9−6 function for the van der Waals (vdW) term and a Coulombic term for an electrostatic interaction. To validate the force field, molecular mechanics calculations and molecular dynamics simulations have been made on a variety of molecules containing the nitrate ester functionality. Excellent agreement has been obtained between the calculated and experimental values for molecular structures, vibrational frequencies, liquid densities, heats of vaporization, crystal structure, mechanical properties, and lattice energy using this force field.