Ab initio and RRKM study of photodissociation of azulene cation.
The ab initio/Rice-Ramsperger-Kassel-Marcus (RRKM) approach has been applied to investigate the photodissociation mechanism of the azulene cation at different values of the photon energy. Reaction pathways leading to various decomposition products have been mapped out at the G3(MP2,CC)//B3LYP level and then the RRKM and microcanonical variational transition state theories have been applied to compute rate constants for individual reaction steps. Relative product yields (branching ratios) for the dissociation products have been calculated using the steady-state approach. The results show that a photoexcited azulene cation can readily isomerize to a naphthalene cation. The major dissociation channels are elimination of atomic hydrogen, an H2 molecule, and acetylene. The branching ratio of the H elimination channel decreases with an increase of the photon energy. The branching ratio of the acetylene elimination as well as that of the H2 elimination rise as the photon energy increases. The main C8H6+ fragment at all photon energies considered is a pentalene cation, and its yield decreases slightly with increasing excitation energy, whereas the branching ratios of the other C8H6+ fragments, phenylacetylene and benzocyclobutadiene cations, grow.
Dyakov
Yu A
YA
Institute of Atomic and Molecular Sciences, Academia Sinica, P.O. Box 23-166, Taipei 10764, Taiwan.
Ni
C-K
CK
Lin
S H
SH
Lee
Y T
YT
Mebel
A M
AM
D052176:Azulenes; D002412:Cations; D003508:Cycloheptanes / Q000737:chemistry* / Q000528:radiation effects; D006859:Hydrogen; D008958:Models, Molecular; D009281:Naphthalenes / Q000737:chemistry; D010777:Photochemistry; D010782:Photolysis; D011084:Polycyclic Aromatic Hydrocarbons
D052176:Azulenes; D002412:Cations; D003508:Cycloheptanes; D009281:Naphthalenes; D011084:Polycyclic Aromatic Hydrocarbons; C031721:naphthalene; D006859:Hydrogen; C005525:azulene