Classical trajectory study of the unimolecular decomposition of H–C≡C–Cl, H–C≡C–H, and Cl–C≡C–Cl

Abstract

Monte Carlo rate constants and lifetime distributions for H–C≡C–H, H–C≡C–Cl, and Cl–C≡C–Cl at 200 kcal/mole were determined by classical trajectories. The Monte Carlo rate constants agree to within 30% of the RRKM prediction. Energy randomization is faster in Cl–C≡C–Cl than in H–C≡C–H and H–C≡C–Cl. An analysis of nonrandom lifetime distributions indicates that energy randomization is complete by 10−12 sec. for each of the molecules. Comparisons are made between our results and other unimolecular studies.