Isotopic replacement in ionic systems: the 4He2+ + 3He -> 3He4He+ + 4He reaction

Full quantum dynamics calculations have been carried out for the ionic reaction 4He2+ + 3He and state-to-state reactive probabilities have been obtained using both a time-dependent (TD) and a time-independent (TI) approach. An accurate ab-initio potential energy surface has been employed for the present quantum dynamics and the two sets of results are shown to be in agreement with each other. The results for zero total angular momentum suggest a marked presence of atom exchange (isotopic replacement) reaction with probabilities as high as 60%. The reaction probabilities are only weakly dependent on the initial vibrational state of the reactants while they are slightly more sensitive to the degree of rotational excitation. A brief discussion of the results for selected higher total angular momentum values is also presented, while the l-shifting approximation [1] has been used to provide estimates of the total reaction rates for the title process. Such rates are found to be large enough to possibly become experimentally accessible

Viscoplasticity and large-scale chain relaxation in glassy-polymeric strain hardening

A simple theory for glassy polymeric mechanical response which accounts for large scale chain relaxation is presented. It captures the crossover from perfect-plastic response to strong strain hardening as the degree of polymerization $N$ increases, without invoking entanglements. By relating hardening to interactions on the scale of monomers and chain segments, we correctly predict its magnitude. Strain activated relaxation arising from the need to maintain constant chain contour length reduces the $N$ dependence of the characteristic relaxation time by a factor $\sim \dot\epsilon N$ during active deformation at strain rate $\dot\epsilon$. This prediction is consistent with results from recent experiments and simulations, and we suggest how it may be further tested experimentally.Comment: The theoretical treatment of the mechanical response has been significantly revised, and the arguments for coherent relaxation during active deformation made more transparen

Fabrication of optically smooth Sn thin films

The fabrication of optically smooth thin Sn films by vacuum or electrodeposition techniques is usually challenging. Little has been published on how to address this challenge mainly because very few applications require such smooth Sn surfaces. The excitation of surface plasmon polaritons on Sn surfaces by prism-based methods represents a case that requires very smooth surfaces and has motivated this work. It is shown that the deposition rate and the substrate temperature of a vacuum evaporation method can be optimized to obtain very smooth Sn films and this is supported by direct imaging evidence from atomic force microscopy and scanning electron microscopy.Comment: 7 figure

The [4+2]‐Cycloaddition of α‐Nitrosoalkenes with Thiochalcones as a Prototype of Periselective Hetero‐Diels–Alder Reactions—Experimental and Computational Studies

The [4+2]‐cycloadditions of α‐nitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styryl‐substituted 4H‐1,5,2‐oxathiazines in moderate to good yields. Of the eight conceivable hetero‐Diels–Alder adducts only this isomer was observed, thus a prototype of a highly periselective and regioselective cycloaddition has been identified. Analysis of crude product mixtures revealed that the α‐nitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bis‐heterocyclic [4+2]‐cycloadducts. The experiments are supported by high‐level DFT calculations that were also extended to related hetero‐Diels–Alder reactions of other nitroso compounds and thioketones. These calculations reveal that the title cycloadditions are kinetically controlled processes confirming the role of thioketones as superdienophiles. The computational study was also applied to the experimentally studied thiochalcone dimerization, and showed that the 1,2‐dithiin and 2H‐thiopyran isomers are in equilibrium with the monomer. Again, the DFT calculations indicate kinetic control of this process

Reconciling Semiclassical and Bohmian Mechanics: III. Scattering states for continuous potentials

In a previous paper [J. Chem. Phys. 121 4501 (2004)] a unique bipolar decomposition, Psi = Psi1 + Psi2 was presented for stationary bound states Psi of the one-dimensional Schroedinger equation, such that the components Psi1 and Psi2 approach their semiclassical WKB analogs in the large action limit. The corresponding bipolar quantum trajectories, as defined in the usual Bohmian mechanical formulation, are classical-like and well-behaved, even when Psi has many nodes, or is wildly oscillatory. A modification for discontinuous potential stationary stattering states was presented in a second paper [J. Chem. Phys. 124 034115 (2006)], whose generalization for continuous potentials is given here. The result is an exact quantum scattering methodology using classical trajectories. For additional convenience in handling the tunneling case, a constant velocity trajectory version is also developed.Comment: 16 pages and 14 figure

Elasticity Theory Connection Rules for Epitaxial Interfaces

Elasticity theory provides an accurate description of the long-wavelength vibrational dynamics of homogeneous crystalline solids, and with supplemental boundary conditions on the displacement field can also be applied to abrupt heterojunctions and interfaces. The conventional interface boundary conditions, or connection rules, require that the displacement field and its associated stress field be continuous through the interface. We argue, however, that these boundary conditions are generally incorrect for epitaxial interfaces, and we give the general procedure for deriving the correct conditions, which depend essentially on the detailed microscopic structure of the interface. As a simple application of our theory we analyze in detail a one-dimensional model of an inhomogeneous crystal, a chain of harmonic oscillators with an abrupt change in mass and spring stiffness parameters. Our results have implications for phonon dynamics in nanostructures such as superlattices and nanoparticles, as well as for the thermal boundary resistance at epitaxial interfaces.Comment: 7 pages, Revte

Cigar Smoking Among U.S. Students: Reported Use After Adding Brands to Survey Items

Background: Among U.S. youth overall, cigars are the most commonly used tobacco product after cigarettes. However, youth who identify their products by brand names, not general terms like “cigar,” may underreport use. Purpose: To examine changes in reported cigar (cigar, cigarillo, or little cigar) smoking among students following inclusion of cigar brand examples on the National Youth Tobacco Survey (NYTS). Methods: Data from the 2011 and 2012 NYTS and National Survey on Drug Use and Health (NSDUH) were analyzed in 2013 to estimate ever and current cigar smoking, overall and by race/ ethnicity. The 2012 NYTS included cigar brand examples (Black and Mild, Swisher Sweets, Dutch Masters, White Owl, Phillies Blunt) in the survey instructions and ever use question, but the 2011 NYTS and 2011 and 2012 NSDUH did not. Results: NYTS ever cigar smoking was higher in 2012 (27.8%) than 2011 (19.5%) among black students overall. Current cigar smoking was 60%–70% higher among black females and students agedZ17 years, in 2012 than 2011. For black females, current cigar smoking (11.5%) was two times greater than that of white females (4.3%) in 2012, whereas the prevalence among these subgroups was comparable in 2011. Similar changes were not observed among these subgroups in the 2011– 2012 NSDUH. Conclusions: This study highlights the high burden of cigar use among U.S. youth and suggests that NYTS ascertainment of cigar smoking may have improved by including brands. Disparities in cigar smoking need to be addressed to prevent and reduce all youth tobacco use. (Am J Prev Med 2014;47(2S1):S28–S35) Published by Elsevier Inc. on behalf of American Journal of Preventive Medicin

FixFit: using parameter-compression to solve the inverse problem in overdetermined models

All fields of science depend on mathematical models. One of the fundamental problems with using complex nonlinear models is that data-driven parameter estimation often fails because interactions between model parameters lead to multiple parameter sets fitting the data equally well. Here, we develop a new method to address this problem, FixFit, which compresses a given mathematical model's parameters into a latent representation unique to model outputs. We acquire this representation by training a neural network with a bottleneck layer on data pairs of model parameters and model outputs. The bottleneck layer nodes correspond to the unique latent parameters, and their dimensionality indicates the information content of the model. The trained neural network can be split at the bottleneck layer into an encoder to characterize the redundancies and a decoder to uniquely infer latent parameters from measurements. We demonstrate FixFit in two use cases drawn from classical physics and neuroscience