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Dissection of the multichannel reaction of acetylene with atomic oxygen: from the global potential energy surface to rate coefficients and branching dynamics

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c8cp07084a· OSTI ID:1598415
 [1];  [1];  [1];  [2];  [3]
  1. Nanjing Univ. (China)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
  3. Nanjing Univ. (China); Univ. of Science and Technology of China, Hefei (China)
+ Show Author Affiliations
The O(3P) + C2H2 reaction is the first step in acetylene oxidation. The accurate kinetic data and the understanding of the reaction dynamics is of great importance. To this end, in this study a full-dimensional global potential energy surface (PES) for the ground triplet state of the O(3P) + C2H2 reaction is constructed based on approximately 85,000 ab initio points calculated at the level of explicitly correlated unrestricted coupled cluster single, double, and perturbative triple excitations with the explicitly correlated polarized valence triple zeta basis set (UCCSD(T)-F12b/VTZ-F12). The PES is fit using the permutation invariant polynomial-neural network (PIP-NN) approach with a total root mean square error of 0.21 kcal mol–1. The key topographic features of the PES, including multiple potential wells and saddle points along different reaction pathways, are well represented by this fit PES. The kinetics and dynamics of the O(3P) + C2H2 reaction are investigated using the quasi-classical trajectory (QCT) method. The calculated rate coefficients are in good agreement with experimental data over a wide temperature range, especially when the temperature is lower than 1500 K. The product branch ratio has also been determined, which indicates the H + HCCO channel as the dominant reaction pathway at 298–3000 K, accounting for 80–90% of the overall rate coefficient, in agreement with experimental observations. The dynamics of the reaction is analyzed in detail.
Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0015997
Other Award/Contract Number:
91641104
21590802
21733006
OSTI ID:
1598415
Alternate ID(s):
OSTI ID: 1489303
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 3 Vol. 21; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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