The heterogeneous uptake of N2O5 on mineral dust particles may play an important role in the removal of nitrogen oxides from the atmosphere. However, the reaction of N2O5 with the mineral particles is not well understood. The reaction of N2O5 with two Si(OH)4 monomers is explored using theoretical methods. This study represents a first step towards understanding the interaction of N2O5 with the hydroxyl groups of silica particles. Energies are calculated using MP2 single point calculations on the B3LYP optimized geometries and including B3LYP thermodynamic corrections. Four mechanisms are considered for the formation of two HNO3 and one H6Si2O7. The rate limiting activation barrier of the most favorable path is found to be 12.5 kcal mol−1. This reaction appears to be more favorable than the hydrolysis of N2O5 with one water molecule. These results are in agreement with experimental observations, which show that N2O5 reacts with OH groups of Saharan dust to form nitrate. © 2012 Wiley Periodicals, Inc.