Microscopic origin of the Baumgärtel-Schausberger-Winter Relaxation Spectrum in Polymer Melts and Particle Rafts

Abstract: Entangled polymer melts exhibit the robust two-branch Baumgärtel-Schausberger-Winter (BSW) relaxation spectrum, while related spectra occur in nonpolymeric monodisperse disordered systems. In spite of the successful application of BSW to many different materials, a molecular derivation of these spectra is lacking. We construct a molecular theory in which a chain segment moves relative to a screened, dynamically responding multichain environment. Gaussian-chain preaveraging gives $M_{\rm seg}(Δm)\sim(Δm)<sup>{-1/2}$, hence $λ_p\sim p<sup>{3/2}$ and, after stress projection, $H(τ)\simτ<sup>{-2/3}$. Independently, longitudinal primitive-path diffusion gives contour-length fluctuations with $H(τ)\simτ<sup>{1/4}$. A molecular-weight-constrained implementation is tested simultaneously against experimental $G&#39;(ω)$ and $G&#39;&#39;(ω)$ data for four monodisperse polybutadiene (PBD) melts, without fitting spectral exponents or individual modal weights. The resulting BSW spectrum exhibits a continuous transfer from the fast cooperative to the slow constraint-renewal cascade before a finite-chain terminal edge. A common two-sector caged dynamics then connects polymers to particle rafts without assuming identical microscopic mechanisms.