Jp. Mcnamara et Ih. Hillier, Exploration of the atmospheric reactivity of N2O5 and HCl in small water clusters using electronic structure methods, PHYS CHEM P, 2(11), 2000, pp. 2503-2509
High level electronic structure calculations have been used to study the ga
s phase reactivity of N2O5 and HCl in small neutral water clusters containi
ng one and two water molecules. The free energy barrier decreases from 61 (
uncatalysed) to 39 kJ mol(-1) when catalysed by two water molecules where t
he reaction products involve ClNO2 and HONO2. A new pathway for the hydroly
sis of N2O5 by a single water is identified with a barrier comparable to th
at for the uncatalysed reaction of N2O5 with HCl. The calculations predict
these reactions may be important in contributing to the ozone destruction c
ycle. However, the calculations also suggest that heterogeneous catalysis w
ill be favoured over the homogeneous process.