Linear viscoelasticity from molecular dynamics simulation of entangled polymers

The linear viscoelastic (LVE) spectrum is one of the primary fingerprints of polymer solutions and melts, carrying information about most relaxation processes in the system. Many single chain theories and models start with predicting the LVE spectrum to validate their assumptions. However, until now, no reliable linear stress relaxation data were available from simulations of multichain systems. In this work, we propose a new efficient way to calculate a wide variety of correlation functions and mean-square displacements during simulations without significant additional CPU cost. Using this method, we calculate stress−stress autocorrelation functions for a simple bead−spring model of polymer melt for a wide range of chain lengths, densities, temperatures, and chain stiffnesses. The obtained stress−stress autocorrelation functions were compared with the single chain slip−spring model in order to obtain entanglement related parameters, such as the plateau modulus or the molecular weight between entanglements. Then, the dependence of the plateau modulus on the packing length is discussed. We have also identified three different contributions to the stress relaxation:  bond length relaxation, colloidal and polymeric. Their dependence on the density and the temperature is demonstrated for short unentangled systems without inertia.

Determination of turbulent heat fluxes using a large aperture scintillometer over undulating mixed agricultural terrain

Scintillometry is an established technique for determining large areal average sensible heat fluxes. The scintillometer measurement is related to sensible heat flux via Monin–Obukhov similarity theory, which was developed for ideal homogeneous land surfaces. In this study it is shown that judicious application of scintillometry over heterogeneous mixed agriculture on undulating topography yields valid results when compared to eddy covariance (EC). A large aperture scintillometer (LAS) over a 2.4 km path was compared with four EC stations measuring sensible (H) and latent (LvE) heat fluxes over different vegetation (cereals and grass) which when aggregated were representative of the LAS source area. The partitioning of available energy into H and LvE varied strongly for different vegetation types, with H varying by a factor of three between senesced winter wheat and grass pasture. The LAS derived H agrees (one-to-one within the experimental uncertainty) with H aggregated from EC with a high coefficient of determination of 0.94. Chronological analysis shows individual fields may have a varying contribution to the areal average sensible heat flux on short (weekly) time scales due to phenological development and changing soil moisture conditions. Using spatially aggregated measurements of net radiation and soil heat flux with H from the LAS, the areal averaged latent heat flux (LvELAS) was calculated as the residual of the surface energy balance. The regression of LvELAS against aggregated LvE from the EC stations has a slope of 0.94, close to ideal, and demonstrates that this is an accurate method for the landscape-scale estimation of evaporation over heterogeneous complex topography.