TY - JOUR
T1 - Unimolecular isomerization/decomposition of ortho-benzyne
T2 - ab initio MO/statistical theory study
AU - Moskaleva, L. V.
AU - Madden, L. K.
AU - Lin, Ming-Chang
PY - 1999/9/1
Y1 - 1999/9/1
N2 - High level molecular-orbital calculations have been carried out to investigate the potential energy surface for the o-benzyne decomposition to 1,3-butadiyne and acetylene as well as that for the isomerization sequence, ortho- to meta- to para-benzyne. The latter species can easily undergo Bergman decyclization. It is shown by statistical theory calculations that the isomerization channel may affect significantly the rate of o-benzyne disappearance in the thermal decomposition process, particularly, at T <2000 K. At 1000 K, the isomerization of o-C6H4 to its m- and p-isomers accounts for as much as 99% of the total disappearance rate. The first order rate coefficients for the production of 1,3-butadiyne, meta- and para-benzynes at 100 Torr, 1 atm and 10 atm pressures over the temperature range 1000-3000 K have been calculated for combustion applications.
AB - High level molecular-orbital calculations have been carried out to investigate the potential energy surface for the o-benzyne decomposition to 1,3-butadiyne and acetylene as well as that for the isomerization sequence, ortho- to meta- to para-benzyne. The latter species can easily undergo Bergman decyclization. It is shown by statistical theory calculations that the isomerization channel may affect significantly the rate of o-benzyne disappearance in the thermal decomposition process, particularly, at T <2000 K. At 1000 K, the isomerization of o-C6H4 to its m- and p-isomers accounts for as much as 99% of the total disappearance rate. The first order rate coefficients for the production of 1,3-butadiyne, meta- and para-benzynes at 100 Torr, 1 atm and 10 atm pressures over the temperature range 1000-3000 K have been calculated for combustion applications.
UR - http://www.scopus.com/inward/record.url?scp=0033198671&partnerID=8YFLogxK
U2 - 10.1039/a902883h
DO - 10.1039/a902883h
M3 - Article
AN - SCOPUS:0033198671
SN - 1463-9076
VL - 1
SP - 3967
EP - 3972
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 17
ER -