TY - JOUR
T1 - Ab initio and RRKM studies of the reactions of C, CH, and 1CH2 with acetylene
AU - Guadagnini, Renee
AU - Schatz, George C.
AU - Walch, Stephen P.
PY - 1998/7/16
Y1 - 1998/7/16
N2 - We present ab initio calculations of geometries, energies, and normal mode frequencies for complexes and saddle points along the minimum energy reaction path for the reaction C + HCCH → C3H2 → C3H + H. We also present ab initio calculations along the minimum energy reaction path in the entrance channel for the reactions C + HCCH, CH + HCCH, and 1CH2 + HCCH. These results and those presented earlier by Walch1 are used to calculate rate constants for the reactions of C, CH, and 1CH2 with acetylene, using variational RRKM theory. The rate constants obtained agree well with experimental results for all three reactions. Unimolecular lifetimes for intermediate complexes associated with each reaction path are also presented. Among the more stable C3 isomers are propargyl and propargylene, which have lifetimes of 25 and 1900 ps, respectively, under thermal reaction conditions.
AB - We present ab initio calculations of geometries, energies, and normal mode frequencies for complexes and saddle points along the minimum energy reaction path for the reaction C + HCCH → C3H2 → C3H + H. We also present ab initio calculations along the minimum energy reaction path in the entrance channel for the reactions C + HCCH, CH + HCCH, and 1CH2 + HCCH. These results and those presented earlier by Walch1 are used to calculate rate constants for the reactions of C, CH, and 1CH2 with acetylene, using variational RRKM theory. The rate constants obtained agree well with experimental results for all three reactions. Unimolecular lifetimes for intermediate complexes associated with each reaction path are also presented. Among the more stable C3 isomers are propargyl and propargylene, which have lifetimes of 25 and 1900 ps, respectively, under thermal reaction conditions.
UR - http://www.scopus.com/inward/record.url?scp=0001252576&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0001252576&partnerID=8YFLogxK
U2 - 10.1021/jp9811070
DO - 10.1021/jp9811070
M3 - Article
AN - SCOPUS:0001252576
SN - 1089-5639
VL - 102
SP - 5857
EP - 5866
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 29
ER -