Understanding the inconsistency between mechanism and rate constants of acetylene ozonolysis

Dongtong Wang; Wang Zelin; Shaowen Zhang

doi:10.1088/1755-1315/358/3/032038

Understanding the inconsistency between mechanism and rate constants of acetylene ozonolysis

Dongtong Wang
, Wang Zelin
, Shaowen Zhang^*

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology

Research output: Contribution to journal › Conference article › peer-review

1 Citation (Scopus)

Abstract

The reaction mechanism of acetylene with ozone was studied by using the complete active space self-consistent-field (CASSCF) and the CASPT2 methods. It was confirmed that the reaction follows the Criegee mechanism, yet a van de Waals complex was introduced in the mechanism. We found the master equation method is the key factor to accurately calculate the rate constants and Arrhenius parameters of this reaction, comparing to the results calculated by the traditional transition state method with steady-state assumption by Cremer which are about an order of magnitude smaller than the experimental data.

Original language	English
Article number	032038
Journal	IOP Conference Series: Earth and Environmental Science
Volume	358
Issue number	3
DOIs	https://doi.org/10.1088/1755-1315/358/3/032038
Publication status	Published - 13 Dec 2019
Event	2019 5th International Conference on Advances in Energy, Environment and Chemical Engineering, AEECE 2019 - Shanghai, China Duration: 16 Aug 2019 → 18 Aug 2019

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title = "Understanding the inconsistency between mechanism and rate constants of acetylene ozonolysis",

abstract = "The reaction mechanism of acetylene with ozone was studied by using the complete active space self-consistent-field (CASSCF) and the CASPT2 methods. It was confirmed that the reaction follows the Criegee mechanism, yet a van de Waals complex was introduced in the mechanism. We found the master equation method is the key factor to accurately calculate the rate constants and Arrhenius parameters of this reaction, comparing to the results calculated by the traditional transition state method with steady-state assumption by Cremer which are about an order of magnitude smaller than the experimental data.",

author = "Dongtong Wang and Wang Zelin and Shaowen Zhang",

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T1 - Understanding the inconsistency between mechanism and rate constants of acetylene ozonolysis

AU - Wang, Dongtong

AU - Zelin, Wang

AU - Zhang, Shaowen

N1 - Publisher Copyright: © Published under licence by IOP Publishing Ltd.

PY - 2019/12/13

Y1 - 2019/12/13

N2 - The reaction mechanism of acetylene with ozone was studied by using the complete active space self-consistent-field (CASSCF) and the CASPT2 methods. It was confirmed that the reaction follows the Criegee mechanism, yet a van de Waals complex was introduced in the mechanism. We found the master equation method is the key factor to accurately calculate the rate constants and Arrhenius parameters of this reaction, comparing to the results calculated by the traditional transition state method with steady-state assumption by Cremer which are about an order of magnitude smaller than the experimental data.

AB - The reaction mechanism of acetylene with ozone was studied by using the complete active space self-consistent-field (CASSCF) and the CASPT2 methods. It was confirmed that the reaction follows the Criegee mechanism, yet a van de Waals complex was introduced in the mechanism. We found the master equation method is the key factor to accurately calculate the rate constants and Arrhenius parameters of this reaction, comparing to the results calculated by the traditional transition state method with steady-state assumption by Cremer which are about an order of magnitude smaller than the experimental data.

UR - https://www.scopus.com/pages/publications/85077218252

U2 - 10.1088/1755-1315/358/3/032038

DO - 10.1088/1755-1315/358/3/032038

M3 - Conference article

AN - SCOPUS:85077218252

SN - 1755-1307

VL - 358

JO - IOP Conference Series: Earth and Environmental Science

JF - IOP Conference Series: Earth and Environmental Science

IS - 3

M1 - 032038

T2 - 2019 5th International Conference on Advances in Energy, Environment and Chemical Engineering, AEECE 2019

Y2 - 16 August 2019 through 18 August 2019

ER -

Understanding the inconsistency between mechanism and rate constants of acetylene ozonolysis

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