Post-transition state dynamics for propene ozonolysis: Intramolecular and unimolecular dynamics of molozonide

Grigoriy Vayner, Srirangam V. Addepalli, Kihyung Song, William L. Hase

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Abstract

A direct chemical dynamics simulation, at the B3LYP/6-31G(d) level of theory, was used to study the post-transition state intramolecular and unimolecular dynamics for the O 3+propene reaction. Comparisons of B3LYP/6-31G(d) with CCSD(T)/cc-pVTZ and other levels of theory show that the former gives accurate structures and energies for the reaction's stationary points. The direct dynamics simulations are initiated at the anti and syn O 3+propene transition states (TSs) and the TS symmetries are preserved in forming the molozonide intermediates. Anti ↔ syn molozonide isomerization has a very low barrier of 2-3 kcal/mol and its Rice-Ramsperger-Kassel-Marcus (RRKM) lifetime is 0.3 ps. However, the trajectory isomerization is slower and it is unclear whether this anti ↔ syn equilibration is complete when the trajectories are terminated at 1.6 ps. The syn (anti) molozonides dissociate to CH 3CHO+H 2COO and H 2CO+syn (anti) CH 3CHOO. The kinetics for the latter reactions are in overall good agreement with RRKM theory, but there is a symmetry preserving non-RRKM dynamical constraint for the former. Dissociation of anti molozonide to CH 3CHO+H 2COO is enhanced and suppressed, respectively, for the trajectory ensembles initiated at the anti and syn O 3+propene TSs. The dissociation of syn molozonide to CH 3CHO+H 2COO may also be enhanced for trajectories initiated at the syn O 3+propene TS. At the time the trajectories are terminated at 1.6 ps, the ratio of the trajectory and RRKM values of the CH 3CHO+H 2COO product yield is 1.6 if the symmetries of the initiation and dissociation TSs are the same and 0.6 if their symmetries are different. There are coherences in the intramolecular energy flow, which depend on molozonide's symmetry (i.e., anti or syn). This symmetry related dynamics is not completely understood, but it is clearly related to the non-RRKM dynamics for anti → syn isomerization and anti molozonide dissociation to CH 3CHO+H 2COO. Correlations are found between the stretching motions of molozonide, indicative of nonchaotic and non-RRKM dynamics. The non-RRKM dynamics of molozonide dissociation partitions vibration energy to H 2COO that is larger than statistical partitioning. Though the direct dynamics simulations are classical, better agreement is obtained using quantum instead of classical harmonic RRKM theory. This may result from the neglect of anharmonicity in the RRKM calculations, the non-RRKM dynamics of the classical trajectories, or a combination of these two effects. The trajectories suggest that the equilibrium syn/anti molozonide ratio is approximately 1.1-1.2 times larger than that predicted by the harmonic densities of state, indicating an anharmonic correction.

Original languageEnglish
Article number014317
JournalJournal of Chemical Physics
Volume125
Issue number1
DOIs
StatePublished - 2006

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