Set Voronoi diagrams of 3D assemblies of aspherical particles

Abstract

Several approaches to quantitative local structure characterization for particulate assemblies, such as structural glasses or jammed packings, use the partition of space provided by the Voronoi diagram. The conventional construction for spherical mono-disperse particles, by which the Voronoi cell of a particle is that of its centre point, cannot be applied to configurations of aspherical or polydisperse particles. Here, we discuss the construction of a Set Voronoi diagram for configurations of aspherical particles in three-dimensional space. The Set Voronoi cell of a given particle is composed of all points in space that are closer to the surface (as opposed to the centre) of the given particle than to the surface of any other; this definition reduces to the conventional Voronoi diagram for the case of mono-disperse spheres. An algorithm for the computation of the Set Voronoi diagram for convex particles is described, as a special case of a Voronoi-based medial axis algorithm, based on a triangulation of the particles’ bounding surfaces. This algorithm is further improved by a pre-processing step based on morphological erosion, which improves the quality of the approximation and circumvents the problems associated with small degrees of particle–particle overlap that may be caused by experimental noise or soft potentials. As an application, preliminary data for the volume distribution of disordered packings of mono-disperse oblate ellipsoids, obtained from tomographic imaging, is computed.     

High-efficiency carrier multiplication and ultrafast charge separation in semiconductor nanocrystals studied via time-resolved photoluminescence

We demonstrate novel methods for the study of multiple exciton generation from a single photon absorption event (carrier multiplication) in semiconductor nanocrystals (or nanocrystal quantum dots) that are complementary to our previously reported transient absorption method. By monitoring the time dependence of photoluminescence (PL) from CdSe nanocrystals via time-correlated single photon counting, we find that carrier multiplication is observable due to the Auger decay of biexcitons. We compare these data with similar studies using transient absorption and find that the two methods give comparable results. In addition to the observation of dynamical signatures of carrier multiplication due to the Auger decay, we observe spectral signatures of multiple excitons produced from the absorption of a single photon. PL spectra at short times following excitation with high-energy photons are red-shifted compared to the single-exciton emission band, which is consistent with previous observations of significant exciton-exciton interactions in nanocrystals. We then show using a combination of transient absorption and time-resolved PL studies that charge transfer between a nanocrystal and a Ru-based catalyst model compound takes place on a time scale that is faster than Auger recombination time constants, which points toward a possible design of donor-acceptor assemblies that can be utilized to take advantage of the carrier multiplication process.     

A computer program for the automatic estimation of H NMR chemical shifts

A computer program has been developed for predicting ¹H NMR chemical shifts. It automatically finds the various substructures of a given molecule for which additivity rules are available. Several strategies have been used to widen the range of applicability. with 200 test compounds, over 90% of the assigned chemical shifts of protons bonded to a carbon atom could be predicted. The mean deviation between observed and predicted values was 0.08 ppm with a standard deviation of 0.19ppm.     

Rejuvenation of PLLA: Effect of plastic deformation and orientation on physical ageing in poly(l‐lactic acid) films

Poly(l ‐lactic acid) (PLLA) is a bio‐degradable polyester which exhibits brittle behaviour due to relatively fast physical ageing of the amorphous phase. This work describes the effects of thermal rejuvenation and molecular orientation of the amorphous phase on this physical ageing process. Uniaxial compression testing showed that physical ageing of the amorphous phase increases the yield stress and the associated strain softening response, both contributing to the observed embrittlement of PLLA in tension. Molecular orientation at constant crystallinity was applied by uniaxial and biaxial plastic deformation just above the glass transition temperature, up to plastic strains of 200% to avoid strain‐induced crystallisation. Using stress‐relaxation experiments combined with tensile testing, both as a function of ageing time, it is shown that both uniaxial and biaxial plastic deformation in excess of 150% plastic strain, decelerates and possibly prohibits the physical ageing process. The oriented monofilaments and films have improved mechanical properties such as stiffness, strength and strain‐to‐break, which were not affected by physical ageing during the whole testing period (40 days). In addition, plastic deformation to higher draw ratios and/or higher temperatures strongly enhanced crystallinity and resulted in PLLA monofilaments and films that also exhibited tough behaviour, not affected by physical ageing. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2233–2244     

New Antifungal `Quinone Methide' Diterpenes from Bobgunnia madagascariensis and Study of Their Interconversion by LC/NMR

Two new `quinone methide' diterpenes with a cassane skeleton were isolated from the root bark of Bobgunnia madagascariensis (Desv. ) J. H. Kirkbr. & Wiersema (Leguminosae). The two compounds occurred as a diastereoisomer mixture 1 / 2 . Their structure was established as (4R,6aS,10aS)‐ and (4S,6aS,10aS)‐ 1,4,6a,7,8,9,10,10a‐octahydro‐4,11‐dihydroxy‐7,7,10a‐trimethyl‐2H‐phenanthro[1,2‐c]pyran‐6,12‐dione by spectroscopic methods and by comparison with the data obtained for another `quinone methide' diterpene isolated previously from the same plant and identified by single‐crystal X‐ray analysis. ¹H‐ and ¹³C‐NMR signals were assigned by extensive in‐mixture 2D correlation experiments, and ¹H‐NMR spectra of the separated diastereoisomers 1 and 2 were recorded by on‐flow LC/NMR. The interconversion of 1 and 2 was followed by repeated stop‐flow LC/NMR experiments over a two‐hour period. Compounds 1 and 2 showed moderate antifungal properties towards human pathogenic fungi, in particular the yeast Candida albicans.     

Utilizing the lability of lead selenide to produce heterostructured nanocrystals with bright, stable infrared emission

Infrared-emitting nanocrystal quantum dots (NQDs) have enormous potential as an enabling technology for applications ranging from tunable infrared lasers to biological labels. Notably, lead chalcogenide NQDs, especially PbSe NQDs, provide efficient emission over a large spectral range in the infrared, but their application has been limited by instability in emission quantum yield and peak position on exposure to ambient conditions. Conventional methods for improving NQD stability by applying a shell of a more stable, wider band gap semiconductor material are frustrated by the tendency of lead chalcogenide NQDs toward Ostwald ripening at even moderate reaction temperatures. Here, we describe a partial cation-exchange method in which we take advantage of this lability to controllably synthesize PbSe/CdSe core/shell NQDs. Critically, these NQDs are stable against fading and spectral shifting. Further, these NQDs can undergo additional shell growth to produce PbSe/CdSe/ZnS core/shell/shell NQDs that represent initial steps toward bright, biocompatible near-infrared optical labels.     

Finite-Data Error Bounds for Koopman-Based Prediction and Control

Journal of Nonlinear Science - This paper presents symmetry reduction for material stochastic Lagrangian systems with advected quantities whose configuration space is a Lie group. Such variational...     

Experiment to measure the Lamb shift in muonic hydrogen

The contribution of the root mean square (RMS) proton charge radius to the Lamb shift (2S–2P energy difference) in muonic hydrogen (μp) amounts to 2%. Apart from the uncertainty on this charge radius, theory predicts the Lamb shift with a precision on the ppm level. We are going to measure ΔE (2 S_1/2(F=1)–2 P_3/2(F=2)) in a laser resonance experiment to a precision of 30 ppm (i.e., 10% of the natural linewidth) and to deduce the RMS proton charge radius with 10⁻³ relative accuracy, 20 times more precise than presently known. The most important requirement for the feasibility of such an experiment, namely the availability of a sufficient amount of long lived metastable μp atoms in the 2S state, has been investigated in a recent experiment at PSI. Our analysis shows that in the order of one percent of all muons stopped in low pressure hydrogen gas form a long lived μp(2S) with a lifetime of the order of 1 μs. The technical realization of our experiment involves a new high intensity low energy muon beam, an efficient low energy muon entrance detector, a randomly triggered 3 stage laser system providing the 0.5 mJ, 7 ns laser pulses at 6.02 μm wavelength, and a combination of a xenon gas proportional scintillation chamber (GPSC) and a microstrip gas chamber (MSGC) with a CsI coated surface to detect the 2 keV X rays from theμp(2P → 1S) transition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Disentangling the K-complex of kaonic hydrogen with DEAR

The DEAR (DAΦNE Exotic Atom Research) experiment at the new φ-factory DAΦNE of Laboratori Nazionali di Frascati aims for a 1% measurement of the line shift of the K-complex due to strong interaction in kaonic hydrogen. This presentation is meant to prove that the high statistics and good resolution obtainable with DEAR will be able to disentangle the kaonic hydrogen K-complex lines (a cascade unconstrained fit), obtaining in this way constraints for what concerns the cascade parameters and, consequently, information regarding the physical processes involved in the kaonic hydrogen atomic cascade. This revised version was published online in August 2006 with corrections to the Cover Date.     

Measurement of the fusion rate in μd3He

Many atomic and molecular processes may occur after a muon has been stopped in a mixture of hydrogen and helium isotopes. In particular, the muonic molecule μd³He can be formed. This molecule either decays or undergoes muon catalyzed fusion. Theory predicts a fusion rate much lower than the decay rate; moreover, the various theoretical predictions differ from each other by several orders of magnitude. With the experiment presented here we intend to measure the effective fusion rate via the detection of the 14.7 MeV fusion proton. A new target and gas mixing system, designed at JINR, were used in a ten-day test run at PSI. The fusion protons and products from other transfer and background reactions were measured with several different detectors (plastic scintillators, BGO, Germanium, neutron, and Silicon detectors). The formation rate of the μd ³He molecule and an upper limit for the effective fusion rate have been measured and are presented here. This revised version was published online in August 2006 with corrections to the Cover Date.