Comparative study of kinetics isomerization of substituted polyacetylene (Cl, F and I): Ab initio and DFT calculations

Ab initio and DFT methods were used to investigate the interconversions of substituted polyacetylene conformers C10H6X6 (X =F, Cl and I) in the vapour phase. The rates of this geometrical isomerization have been calculated and the Arrhenius parameters evaluated. In the case of unsubstituted polyacetylene as the reference, the B3LYP Arrhenius parameters obtained are A1 =2.99 · 10^17 s^–1 and Ea= 17.30 kcal mol^–1. The values of the equilibrium constant for the reaction have also been determined at various temperatures between 300 and 500 K and the value of the energies change calculated. The results also suggest that the straightforward kinetics characterizing the majority of substituted polyacetylene isomerizations above 300 K. The isomerization energies are positive and the barrier heights ΔEbarrier are expected to be sensitive for the magnitude of halogens effects. According to geometries features the Cis rightarrow Trans isomerization in the gas phase occurs by a rotational mechanism.