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Title: Nascent energy distribution of the Criegee intermediate CH 2OO from direct dynamics calculations of primary ozonide dissociation

Here, 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-C 2H 4O 3, 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 (H 2COO) and formaldehyde (H 2CO). 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 newhigh-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,more » 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. Published by AIP Publishing.« less
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [2] ; ORCiD logo [3]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Stuttgarg, Stuttgart (Germany)
  2. Texas Tech Univ., Lubbock, TX (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 17; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); Air Force Research Laboratory (AFRL), Air Force Office of Scientific Research (AFOSR); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1461495
Alternate Identifier(s):
OSTI ID: 1436013

Pfeifle, Mark, Ma, Yong -Tao, Jasper, Ahren W., Harding, Lawrence B., Hase, William L., and Klippenstein, Stephen J.. Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation. United States: N. p., Web. doi:10.1063/1.5028117.
Pfeifle, Mark, Ma, Yong -Tao, Jasper, Ahren W., Harding, Lawrence B., Hase, William L., & Klippenstein, Stephen J.. Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation. United States. doi:10.1063/1.5028117.
Pfeifle, Mark, Ma, Yong -Tao, Jasper, Ahren W., Harding, Lawrence B., Hase, William L., and Klippenstein, Stephen J.. 2018. "Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation". United States. doi:10.1063/1.5028117.
@article{osti_1461495,
title = {Nascent energy distribution of the Criegee intermediate CH2OO from direct dynamics calculations of primary ozonide dissociation},
author = {Pfeifle, Mark and Ma, Yong -Tao and Jasper, Ahren W. and Harding, Lawrence B. and Hase, William L. and Klippenstein, Stephen J.},
abstractNote = {Here, 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 newhigh-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. Published by AIP Publishing.},
doi = {10.1063/1.5028117},
journal = {Journal of Chemical Physics},
number = 17,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

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