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Title: Computational Study of the HCCO + NO Reaction: ab Initio MO/vRRKM Calculations of the Total Rate Constant and Product Branching Ratios
Journal: J. Phys. Chem. A
Volume: 107
Page(s): 1066 - 1076
Year: 2003
Reference type: Journal article
Squib: 2003TOK/MOS1066-1076
Reaction:
NO + HCCO → HCN + CO2
Reaction order:
2
Reference reaction:
NO + HCCO → Products
Reference reaction order:
2
Rate expression:
no rate data available
Category: Theory
Data type:
Ab initio
Comments:
Rate constant given in double exponential form for branching ratio of HCCO + NO -> HCN + CO2 channel versus total products. k = 0.5*exp(-T/67.1) + 0.3*exp(-T/2592)
Quantum chemical study. Rate constants derived from transition states using NIST ChemRate and Truhlars Polyrate programs. Geometry optimization done using B3LYP/6-311G(d,p). Energies obtained at levels upto QCISD(T) and CCSD(T)/6-311+G(3df,2p).
HCCO + NO first forms intermediate O=N-CH=C=O (nitrosoketene). This may decompose to form HCNO + CO or a cyclic compound -N=CH-C(O)- (Oxazetone). This cyclic compound then may decompose to for HCN + CO2. Good agreement between calculated rate constants for HCCO + NO -> PRODUCTS with experimental data, as well as branching ratios for HCNO + CO versus HCN + CO2 channels.
NOTE paper calls HNCO Fulminic acid which has a structural formula of C#N-OH. However, molecule HCNO in paper appears to be Nitrosomethylene HC-N=O looking back on work by others referenced in the paper.
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