Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation
Abstract
Ozonolysis produces chemically activated carbonyl oxides (Criegee intermediates, CIs) that are either stabilized or decompose directly. This branching has an important impact on atmospheric chemistry. Prior theoretical studies have employed statistical models for energy partitioning to the CI arising from dissociation of the initially formed primary ozonide (POZ). Here, we used direct dynamics simulations to explore this partitioning for decomposition of c–C2H4O3, the POZ in ethylene ozonolysis. A priori estimates for the overall stabilization probability were then obtained by coupling the direct dynamics results with master equation simulations. Trajectories were initiated at the concerted cycloreversion transition state, as well as the second transition state of a stepwise dissociation pathway, both leading to a CI (H2COO) and formaldehyde (H2CO). The resulting CI energy distributions were incorporated in master equation simulations of CI decomposition to obtain channel-specific stabilized CI (sCI) yields. Master equation simulations of POZ formation and decomposition, based on new high-level electronic structure calculations, were used to predict yields for the different POZ decomposition channels. A non-negligible contribution of stepwise POZ dissociation was found, and new mechanistic aspects of this pathway were elucidated. By combining the trajectory-based channel-specific sCI yields with the channel branching fractions, an overall sCI yield of (48 ± 5)% was obtained. Non-statistical energy release was shown to measurably affect sCI formation, with statistical models predicting significantly lower overall sCI yields (∼30%). Within the range of experimental literature values (35%-54%), our trajectory-based calculations favor those clustered at the upper end of the spectrum.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- May 04, 2018
- Source ID
- 10.1063/1.5028117
Entities
People
- Ahren W Jasper
- Lawrence B Harding
- Mark Pfeifle
- Stephen Klippenstein
- William L Hase
- Yong-Tao Ma
Organizations
- Air Force Office of Scientific Research
- Argonne National Laboratory
- German Academic Exchange Service
- National Science Foundation
- Robert A. Welch Foundation
- Texas Tech University
- United States Department of Energy