In this project we are carrying out high level ab initio molecular orbital calculations of reaction pathways of NO_x reactions that may be occurring in nuclear waste storage tanks. The computations will be used to calculate equilibrium structures of reactants and products of oxidizing NO_x radical anions in order to determine free energies for possible reactions. In addition, activation energies will be calculated for transition states to help determine rates for the reactions. The methods used in these calculations include Gaussian-2 (G2), theory which has been shown to provide accurate reaction energies. In some cases the energetics will be measurable by uniquely capable pulse radiolysis experiments, while in others computation will provide the only known determinations. Theory and experiment will be closely coupled. We will also use density functional theory for systems which are too large to address with G2 theory. Solvation effects will be included using contiuum models.

This is a new project; we will add a description of our progress as it becomes available.