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

VL - 1

SP - 3967

EP - 3972

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 17

ER -