Interpretation of quasi-elastic light scattering data for flexible chains: model dependence

The autocorrelation functions and corresponding relaxation times obtained from the forward depolarized quasi-elastic light scattering experiment are exhibited for two quite similar models of flexible polymer chains in solution. A very small change in the chain dynamics is found to be sufficient to change the relaxation time from a relatively short time independent of chain length, with an autocorrelation function suggestive of an unweighted sum of contributions from all the relaxation times in the spectrum of chain motion, to a long time with an autocorrelation function identical with that for the end-to-end vector, strongly dependent upon chain length and dominated by the longest relaxation time in the spectrum. These results raise the question whether widely-used models in which information about short-range chain structure and motion is deliberately omitted can be expected to be appropriate for the interpretation of depolarized scattering experiments.