期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 126, 期 12, 页码 1946-1959出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.1c10860
关键词
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资金
- Key Lab of Functional Crystals and Laser Technology of TIPC, CAS
- National Key R&D Program of China [2020YFA0714500]
- High-tech Discipline Construction Fundings for Universities in Beijing (Safety Science and Engineering)
- Beijing Key Laboratory of City Integrated Emergency Response Science
This study provides a highly accurate investigation of the initial reaction in methane combustion, presenting a potential energy surface and revealing a detailed mechanism. The findings are significant for improving our understanding of the primary process in hydrocarbon combustion.
Methane combustion plays an important role in various fields such as combustion chemistry and atmospheric chemistry of the stratosphere. Highly accurate study of its initial reaction remains a key challenge. Here, through extensive studies with a state-of-the-art ab initio and neural network method, we present a potential energy surface of the O(P-3) + CH4 -> OH + CH3 reaction on the ground state 1(3)A and the first excited state 2(3)A. In this work, the energies of 10 167 points covering all important regions are obtained with state-averaged complete active space self-consistent field calculations and then fitted using the Levenberg- Marquardt algorithm with a root-mean-square error of 0.391 and 0.442 kcal/mol for the 1(3)A and 2(3)A states, respectively. This study explores the characteristics of the radical van der Waals (VdW) complex and reveals a detailed mechanism of the methane combustion initial reaction. Within the scope of this mechanism, this surface gives a fairly accurate description of the regions around the saddle point, conical intersection, and vdW wells in the entrance for efficient computational simulations. As a theoretical study on a prototypical polyatomic reaction, it is hopeful that this work will modify our understanding of the primary process in hydrocarbon combustion.
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