On the dynamics of state selected unimolecular reactions: Chloroacetylene dissociation and predissociation

Classical trajectories have been used to investigate the dynamics of chloroacetylene dissociation and predissociation. Monte Carlo techniques were used to study dissociation from initial state selected energy distributions. Calculations using different initial distributions show that on a 10 ^-12 sec time scale the HC stretch internal coordinate is decoupled from the remaining internal coordinates. A simulation of chloroacetylene dissociation following S₁→S₀ internal conversion gives a rate constant in agreement with the RRKM theory. A comparison is made between these results and experimental ones.