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Author(s):   Liu, Y.Z.; Zhang, Z.Q.; Pei, L.S.; Chen, Y.; Chen, C.X.
Title:   Reaction kinetic studies of CCl2 with C2H2 and H2O molecules
Journal:   Chem. Phys.
Volume:   303
Page(s):   255 - 263
Year:   2004
Reference type:   Journal article
Squib:   2004LIU/ZHA255-263

Reaction:   M + C2H2 + CCl2 (X 1A1) → M + Products
Reaction order:   3
Temperature:   293 K
Pressure:  1.60E-2 bar
Rate expression:   8.3x10-32 [cm6/molecule2 s]
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure dependent
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Laser induced fluorescence
Comments:   Ground state CCl2 was produced by photolysis of CCl4 at 213 nm. The decays of CCl2 were then monitored with LIF in the presence of the substrate to determine the kinetics.

The reaction mechanism was explored with ab initio calculations. Geometries of reactants, products, intermediates, and transition states were optimized at B3LYP/6-31G(d) level and energies, frequencies and ZPEs are reported. A three center cycloaddition to the triple bond is found to be the favored reaction and the the barrier is calculated to be 5.7 kcal/mol. Insertion of CCl2 into the C-H bond has a calculated barrier of 26.3 kcal/mol.

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