Melt viscosities of lattice polymers using a Kramers potential treatment

Kramers relaxation times $\tau_{K}$ and relaxation times $\tau_{R}$ and $\tau_{G}$ for the end-to-end distances and for center of mass diffusion are calculated for dense systems of athermal lattice chains. $\tau_{K}$ is defined from the response of the radius of gyration to a Kramers potential which approximately describes the effect of a stationary shear flow. It is shown that within an intermediate range of chain lengths N the relaxation times $\tau_{R}$ and $\tau_{K}$ exhibit the same scaling with N, suggesting that N-dependent melt-viscosities for non-entangled chains can be obtained from the Kramers equilibrium concept.Comment: submitted to: Journal of Chemical Physic

Superhalogen and Superacid

A superhalogen $\rm{F@C_{20}(CN)_{20}}$ and a corresponding Br{\o}nsted superacid were designed and investigated on DFT and DLPNO-CCSD(T) levels of theory. Calculated compounds have outstanding electron affinity and deprotonation energy, respectively. We consider superacid $\rm{H[F@C_{20}(CN)_{20}]}$ to be able to protonate molecular nitrogen. The stability of these structures is discussed, while some of the previous predictions concerning Br{\o}nsted superacids of record strength are doubted.Comment: 11 pages (main paper), 32 pages (supporting information), 10 figures, 10 tables, 62 reference

Polyethylene under tensile load: strain energy storage and breaking of linear and knotted alkanes probed by first-principles molecular dynamics calculations

The mechanical resistance of a polyethylene strand subject to tension and the way its properties are affected by the presence of a knot is studied using first-principles molecular dynamics calculations. The distribution of strain energy for the knotted chains has a well-defined shape that is very different from the one found in the linear case. The presence of a knot significantly weakens the chain in which it is tied. Chain rupture invariably occurs just outside the entrance to the knot, as is the case for a macroscopic rope.Comment: 8 pages, 11 figures, to appear on J. Chem. Phy

Performance characteristics of wind profiling radars

Doppler radars used to measure winds in the troposphere and lower stratosphere for weather analysis and forecasting are lower-sensitivity versions of mesosphere-stratosphere-troposphere radars widely used for research. The term wind profiler is used to denote these radars because measurements of vertical profiles of horizontal and vertical wind are their primary function. It is clear that wind profilers will be in widespread use within five years: procurement of a network of 30 wind profilers is underway. The Wave Propagation Laboratory (WPL) has operated a small research network of radar wind profilers in Colorado for about two and one-half years. The transmitted power and antenna aperture for these radars is given. Data archiving procedures have been in place for about one year, and this data base is used to evaluate the performance of the radars. One of the prime concerns of potential wind profilers users is how often and how long wind measurements are lacking at a given height. Since these outages constitute an important part of the performance of the wind profilers, they are calculated at three radar frequencies, 50-, 405-, and 915-MHz, (wavelengths of 6-, 0.74-, and 0.33-m) at monthly intervals to determine both the number of outages at each frequency and annual variations in outages

Electromagnetic Vacuum of Complex Media: Dipole Emission vs. Light Propagation, Vacuum Energy, and Local Field Factors

We offer a unified approach to several phenomena related to the electromagnetic vacuum of a complex medium made of point electric dipoles. To this aim, we apply the linear response theory to the computation of the polarization field propagator and study the spectrum of vacuum fluctuations. The physical distinction among the local density of states which enter the spectra of light propagation, total dipole emission, coherent emission, total vacuum energy and Schwinger-bulk energy is made clear. Analytical expressions for the spectrum of dipole emission and for the vacuum energy are derived. Their respective relations with the spectrum of external light and with the Schwinger-bulk energy are found. The light spectrum and the Schwinger-bulk energy are determined by the Dyson propagator. The emission spectrum and the total vacuum energy are determined by the polarization propagator. An exact relationship of proportionality between both propagators is found in terms of local field factors. A study of the nature of stimulated emission from a single dipole is carried out. Regarding coherent emission, it contains two components. A direct one which is transferred radiatively and directly from the emitter into the medium and whose spectrum is that of external light. And an indirect one which is radiated by induced dipoles. The induction is mediated by one (and only one) local field factor. Regarding the vacuum energy, we find that in addition to the Schwinger-bulk energy the vacuum energy of an effective medium contains local field contributions proportional to the resonant frequency and to the spectral line-width.Comment: Typos fixed, journal ref. adde

Scaled Particle Theory for Hard Sphere Pairs. I. Mathematical Structure

We develop an extension of the original Reiss-Frisch-Lebowitz scaled particle theory that can serve as a predictive method for the hard sphere pair correlation function g(r). The reversible cavity creation work is analyzed both for a single spherical cavity of arbitrary size, as well as for a pair of identical such spherical cavities with variable center-to-center separation. These quantities lead directly to prediction of g(r). Smooth connection conditions have been identified between the small-cavity situation where the work can be exactly and completely expressed in terms of g(r), and the large-cavity regime where macroscopic properties become relevant. Closure conditions emerge which produce a nonlinear integral equation that must be satisfied by the pair correlation function. This integral equation has a structure which straightforwardly generates a solution that is a power series in density. The results of this series replicate the exact second and third virial coefficients for the hard sphere system via the contact value of the pair correlation function. The predicted fourth virial coefficient is approximately 0.6 percent lower than the known exact value. Detailed numerical analysis of the nonlinear integral equation has been deferred to the sequel (following paper