Accurate effective pair potentials for polymer solutions

Dilute or semi-dilute solutions of non-intersecting self-avoiding walk (SAW) polymer chains are mapped onto a fluid of ``soft'' particles interacting via an effective pair potential between their centers of mass. This mapping is achieved by inverting the pair distribution function of the centers of mass of the original polymer chains, using integral equation techniques from the theory of simple fluids. The resulting effective pair potential is finite at all distances, has a range of the order of the radius of gyration, and turns out to be only moderately concentration-dependent. The dependence of the effective potential on polymer length is analyzed in an effort to extract the scaling limit. The effective potential is used to derive the osmotic equation of state, which is compared to simulation data for the full SAW segment model, and to the predictions of renormalization group calculations. A similar inversion procedure is used to derive an effective wall-polymer potential from the center of mass density profiles near the wall, obtained from simulations of the full polymer segment model. The resulting wall-polymer potential turns out to depend strongly on bulk polymer concentration when polymer-polymer correlations are taken into account, leading to a considerable enhancement of the effective repulsion with increasing concentration. The effective polymer-polymer and wall-polymer potentials are combined to calculate the depletion interaction induced by SAW polymers between two walls. The calculated depletion interaction agrees well with the ``exact'' results from much more computer-intensive direct simulation of the full polymer-segment model, and clearly illustrates the inadequacy -- in the semi-dilute regime -- of the standard Asakura-Oosawa approximation based on the assumption of non-interacting polymer coils.Comment: 18 pages, 24 figures, ReVTeX, submitted to J. Chem. Phy

Towards modular compilers for effects

Compilers are traditionally factorised into a number of separate phases, such as parsing, type checking, code generation, etc. However, there is another potential factorisation that has received comparatively little attention: the treatment of separate language features, such as mutable state, input/output, exceptions, concurrency and so forth. In this article we focus on the problem of modular compilation, in which the aim is to develop compilers for separate language features independently, which can then be combined as required. We summarise our progress to date, issues that have arisen, and further wor

Cryogenic infrared spectroscopy provides mechanistic insight into the fragmentation of phospholipid silver adducts

Tandem mass spectrometry is arguably the most important analytical tool for structure elucidation of lipids and other metabolites. By fragmenting intact lipid ions, valuable structural information such as the lipid class and fatty acyl composition are readily obtainable. The information content of a fragment spectrum can often be increased by the addition of metal cations. In particular, the use of silver ions is deeply rooted in the history of lipidomics due to their propensity to coordinate both electron-rich heteroatoms and C = C bonds in aliphatic chains. Not surprisingly, coordination of silver ions was found to enable the distinction of sn-isomers in glycerolipids by inducing reproducible intensity differences in the fragment spectra, which could, however, not be rationalized. Here, we investigate the fragmentation behaviors of silver-adducted sn- and double bond glycerophospholipid isomers by probing fragment structures using cryogenic gas-phase infrared (IR) spectroscopy. Our results confirm that neutral headgroup loss from silver-adducted glycerophospholipids leads to dioxolane-type fragments generated by intramolecular cyclization. By combining high-resolution IR spectroscopy and computational modelling of silver-adducted fragments, we offer qualitative explanations for different fragmentation behaviors of glycerophospholipid isomers. Overall, the results demonstrate that gas-phase IR spectroscopy of fragment ions can significantly contribute to our understanding of lipid dissociation mechanisms and the influence of coordinating cations

Effect of root spacing on interpretation of blade penetration tests-full-scale physical modelling

The spatial distribution of plant roots is an important parameter when the stability of vegetated slopes is to be assessed. Previous studies in both laboratory and field conditions have shown that a penetrometer adapted with a blade-shaped tip can be used to detect roots from sudden drops in penetrometer resistance. Such drops can be related to root properties including diameter, stiffness and strength using simpleWinkler foundation models, thereby providing a field instrument for rapid quantification of root properties and distribution. While this approach has proved useful for measuring single widely-spaced roots, it has not previously been determined how the penetrometer response changes as a result of roots being in close proximity. Therefore in this study 1-g physical modelling (at 1:1 scale) was conducted to study the effect of vertical root spacing using horizontal, straight 3D-printed root analogues. Results showthatwhen roots are closely spaced, there is significant interaction between them, resulting in higher apparent root displacements to failure and an increased amount of energy being dissipated. This preliminary work shows that the interpretive models used to analyse the penetrometer trace require further development to account for root-soil-root interactions in densely rooted soil.</p

Comparison of new <i>in situ </i>root-reinforcement measuring devices to existing techniques

Mechanical root-reinforcement is difficult to quantify. Existing in-situ methods are cumbersome, while modelling requires parameters which are difficult to acquire. In this paper, two new in-situ measurement devices are introduced ('cork screw' and 'pin vane') and their performance is compared to field vane and laboratory direct shear strength measurements in fallow and rooted soil. Both new methods show a close correlation with field vane readings in fallow soil. Tests in reinforced soil show that both new methods can be installed without significant root disturbance. The simplicity of both new methods allows for practical in-situ use and both can be used to study soil stress-strain behaviour, thus addressing some major limitations in existing methodologies for characterising rooted soil.</p

Volumetric rheology of polymers

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Nonresonant EFISH and THG studies of nonlinear optical property and molecular structure relations of benzene, stilbene, and other arene derivatives

D.c. elec. field induced 2nd-harmonic generation (EFISH) and 3rd-harmonic generation (THG) measurement results are reported on the intrinsic mol. hyperpolarizabilities of benzenes, stilbenes, and other arene derivs. Structure-property relations, as revealed by a comprehensive set of systematic measurements, are discussed. Issues concerning donor-acceptor strength; charge-transfer; transparency trade-off; conjugation planarity, length, and aromaticity; and heteroatom and side-group substitution effects are included

Optical properties of an ensemble of G-centers in silicon

We addressed the carrier dynamics in so-called G-centers in silicon (consisting of substitutional-interstitial carbon pairs interacting with interstitial silicons) obtained via ion implantation into a silicon-on-insulator wafer. For this point defect in silicon emitting in the telecommunication wavelength range, we unravel the recombination dynamics by time-resolved photoluminescence spectroscopy. More specifically, we performed detailed photoluminescence experiments as a function of excitation energy, incident power, irradiation fluence and temperature in order to study the impact of radiative and non-radiative recombination channels on the spectrum, yield and lifetime of G-centers. The sharp line emitting at 969 meV ($\sim$1280 nm) and the broad asymmetric sideband developing at lower energy share the same recombination dynamics as shown by time-resolved experiments performed selectively on each spectral component. This feature accounts for the common origin of the two emission bands which are unambiguously attributed to the zero-phonon line and to the corresponding phonon sideband. In the framework of the Huang-Rhys theory with non-perturbative calculations, we reach an estimation of 1.6$\pm$0.1 \angstrom for the spatial extension of the electronic wave function in the G-center. The radiative recombination time measured at low temperature lies in the 6 ns-range. The estimation of both radiative and non-radiative recombination rates as a function of temperature further demonstrate a constant radiative lifetime. Finally, although G-centers are shallow levels in silicon, we find a value of the Debye-Waller factor comparable to deep levels in wide-bandgap materials. Our results point out the potential of G-centers as a solid-state light source to be integrated into opto-electronic devices within a common silicon platform