Theoretical investigation of the decarboxylation reaction of CH3CO2 radical

Yu Zhi Zhou, Se Li, Qian Shu Li*, Shao Wen Zhang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

A theoretical study on the decarboxylation reaction of CH3CO2 radical at the MP2 level of theory has been carried out. It is found that the thermal reaction CH3CO2 → CH3 + CO2 may occur on the 2A′(A′) potential energy surface of CH3CO2 via a reaction barrier of 4.2 kcal/mol at the PMP4/6-311+G(3df,3pd)//MP2/6-311+G(2df,2p) level of theory. Another possible reaction path is the CH3CO2(A′) transform into the CH3CO2(A1) and thus undergo a barrier-less dissociation into the products CH3 + CO2. The thermal rate constants of channel CH3CO2(A′) → CH3 + CO2.were evaluated based on the electronic structure and energy information from the PMP4/6-311+G(3df,3pd)//MP2/6-311+G(2df,2p) level of theory with microcanonical variational transition state theory (μVT) in the temperature range of 200-3000 K. The fitted Arrhenius expression from the forward μVT rate constants within the calculated temperature range is Kμ VT = 2.196 × 1011 T0.294 e(- 2.304 × 103 / T) s- 1. It is also found that the geometry of the CH3CO2 radical is sensitive to the basis set used.

Original languageEnglish
Pages (from-to)40-45
Number of pages6
JournalJournal of Molecular Structure: THEOCHEM
Volume854
Issue number1-3
DOIs
Publication statusPublished - 15 Apr 2008

Fingerprint

Dive into the research topics of 'Theoretical investigation of the decarboxylation reaction of CH3CO2 radical'. Together they form a unique fingerprint.

Cite this