The reaction of N 2 O 5 with H 3 O + : A first‐principles direct molecular dynamics study of acid‐catalyzed reactive uptake of N 2 O 5

Direct molecular dynamics simulations of N 2 O 5 + H 3 O + collision were conducted; (1) to assess the importance of acid‐catalyzed N 2 O 5 decomposition paths expected to play a significant role in the chemistry of stratospheric ozone depletion and (2) for their potential to identify unexpected decomposition paths. A single H 3 O + ‐catalyzed N 2 O 5 decomposition path was observed. Products formed are H 2 O, NO   2 + , HNO 3 , and complexes of the decomposition products, (H 2 O)(NO   2 + ), (H 2 O)(HNO 3 ), and (HNO 3 )(NO   2 + ). All decompositions were barrierless, including complex formations of the products. Reaction exothermicities, which were characterized with a QCISD(T)/6‐311++G(d,p)//MP2/6‐311++G(d,p) model, ranged from 5.9 to 32.0 kcal/mol. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009