SynopsisThe intermediate scattering function G ( K , t ) for any polymer model obeying a linear separable Langevin equation can be expressed in terms of the eigenvalues and eigenvectors of its normal coordinate transformation. An algorithm for the exact numerical evaluation of G ( K , t ) for linear Rouse-Zimm chains in the presence of hydrodynamic interaction has been developed. The computed G ( K , t ) 2 were fit to C ( t ) = A exp(-t/TA) + B, and apparent diffusion coefficients calculated according to Dapp = 1/(27,4K2). G(K,t)2 was surprisingly well-fit by single-exponential decays, especially a t both small and large values of Kb, where K is the scattering vector and b the root-mean-squared subunit extension. Plots of D,,, vs K 2 invariably showed a sigmoidal rise from Do a t K 2 = 0 up to a constant plateau value a t large K2b2.Analytical expressions for G(K,t), exact in the limit of short times, were obtained for circularRouse-Zimm chains with and without hydrodynamic interaction, and also for free-draining linear chains, and in addition for the independent-segment-mean-force (ISMF) model. The predicted behavior for G(K,t) a t large Kb (or KRc) was found in all cases to be single-exponential with ~/ T A a K 2 a t large Kb, in agreement with the computational results. A simple procedure for estimating all parameters of the Rouse-Zimm model from a plot of Dapp vs K 2 is proposed. Experimental data for both native and pH-denatured calf-thymus DNA in 1.OM NaCl with and without EDTA clearly exhibit plateau behavior of D,,, a t large values of K , in harmony with the present Rouse-Zimm and ISMF theories, and in sharp contrast to previous predictions based on the Rouse-Zimm model.