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Title: Experimental and Computational Studies of the Kinetics and Mechanisms for C6H5 Reactions with Acetone -h6 and -d6
Journal: J. Phys. Chem. A
Volume: 107
Page(s): 7755 - 7761
Year: 2003
Reference type: Journal article
Squib: 2003CHO/PAR7755-7761
Reaction:
(CH3)2CO + Phenyl → C6H5C(O*)(CH3)2
Reaction order:
2
Rate expression:
no rate data available
Category: Theory
Data type:
Ab initio
Comments:
Combined experimental and quantum study. C6H5 produced by 248 nm KrF excimer laser photolysis of C6H5NO. C6H5 detected using cavity ring down spectroscopy at 504.8 nm versus time. Typical acetone 0-0.35 torr in 20-75 torr Argon. Used both acetone and deuterated acetone (d6).
DFT quantum calculations B3LYP/aug-cc-pvTZ energies. Rate expressions calculated using Truhlars Polyrate program. Tunneling correction CVT/SCT employed.
Quantum calculations found abstraction barrier of about 3.9 kcal/mol, C addition channel with barrier of about 9.4 kcal/mol, and O addition channel with barrier of about 12.4 kcal/mol. Thus, abstraction dominates. C addition channel can lead to beta scission of CH3 and formation of methyl phenyl ketone with calculated barrier of about 8.1 kcal/mol
Calculated barrier height of 9.4 kcal/mol
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