甲基触发苯乙炔生成双环芳烃茚的动力学反应机理OA

In order to reveal the formation mechanism of the bicyclic aromatic hydrocarbon indene,the re-action potential energy surface of methyl radical and phenylacetylene was studied,and the kinetic data were calculated.Firstly,the B3LYP/6-311+G(d,p)method was used to optimize the geometry and analyze the vibration frequency of all species in the reaction system of phenylacetylene and methyl radical.Then,the CCSD(T)/aug-cc-pVDZ method was used to obtain high-precision energy of each species.Finally,reac-tion rate constants and branching ratios of important paths were ultimately computed by the time-dependent RRKM/ME theory.Theoretical results indicated that the addition of methyl radical onto the acetylenyl group in phenylacetylene would trigger the subsequent isomerization and dissociation.And on variable pres-sure(0.001～0.1 MPa)and temperature(300～3 000 K)conditions,1-phenyl-1-propyne(C9H8)+H were invariably the main product for current system.Moreover,the low pressures conduced to yield indene,and its formation were competing fiercely for the bimolecular products,i.e.C6H5+C3H4,C6H5+C3H4-2 and Int41-P4+C2H2,while high pressures were in favor of these bimolecular products generated.