Relaxation times in transient electric birefringence and electric‐field light scattering of flexible polymer chains

We study in the present paper the response of a flexible macromolecular chain to the application or removal of an electric field. The polymer is mainly modeled as a Gaussian chain, and the case of freely jointed chains is also treated. We consider the dynamics of the chains, after the inception and subsequent cessation of an electric field. In particular, we calculate two properties. One of them is the time‐dependent chain expansion, as measured by the components of the gyration tensor, that can be determined by transient electric‐field light scattering. The other property is the transient electric birefringence, related to the reorientation of the chain segments. In this way, the dynamics of two different properties can be compared. The transient properties are analyzed in terms of a series of relaxation times. We propose the use of a mean relaxation time as a convenient representation of the rate of the dynamic process, and show that it can be deduced from simulation or experiments with more accuracy than the longest relaxation time. Our computational procedure is based on Brownian dynamics simulation. For Gaussian chains without hydrodynamic interaction, the results are compared with the predictions from the Rouse theory. We evaluate the influence of the strength of the force or field. Simulations are also carried out including hydrodynamic interactions, so that the importance of this effect can be assessed. We propose some combination of relaxation times with other macromolecular properties that take universal numerical values.