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Author(s):   Che, C.-b.; Zhang, H.; Zhang, X.; Liu, Y.; Liu, B.
Title:   Ab Initio and Kinetic Study on CH3 Radical Reaction with H2CO
Journal:   J. Phys. Chem. A
Volume:   107
Page(s):   2929 - 2933
Year:   2003
Reference type:   Journal article
Squib:   2003CHE/ZHA2929-2933

Reaction:   CH2O + ·CH3CH3OCH2
Reaction order:   2
Rate expression:   no rate data available
Category:  Theory
Data type:   Ab initio
Pressure dependence:   Rate constant is high pressure limit
Comments:   Quantum calculations of reaction of CH3 with CH2O. Calculated geometries at B3LYP/6-311+G(d,p) and energies at CCSD(T)/6-311G(2df,p). Also calculated energetics at B3LYP and G2 levels. Use Truhlars Polyrate program to calculate rate expressions using CVT/SCT tunneling corrections.

Considered abstraction, carbon addition, and oxygen addition channels. Abstraction dominates over addition channels by factor of 10 over carbon addition and many orders of magnitude over oxygen addition channel. Found carbon addition channel can contribute at lower temperatures. Agreement with experimental measurements is good (factor of 2 higher) with some and only fair with others (factor of 5-10 higher). Depends on temperature range and the specific measurement.

Calculated barriers are 40 kcal/mol for abstraction, 34 kcal/mol for C addition, and 69 kcal/mol for O addition channels. Although abstraction has higher barrier than C addition, it also has larger prefactor.

Fits given here in database are NIST fits to curves in Figure 3 in paper. Rate expressions NOT given in paper.

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