Chain-length dependent termination in pulsed-laser polymerization .1. Interaction with propagation

Using a new simulation procedure in which each individual propagation step is subjected to a Poisson process it was proved that in case of chain-length dependent termination the apparent rate of propagation no longer coincides with the true one. This is caused by the polydispersity of the chain-length distribution of the growing chains: shorter chains are removed preferentially. This effect is comparatively small although significant. The consequences for the determination of the rate constant of chain propagation k(p) are nearly negligible.