Determination of differential elastic and vibrational excitation cross sections for e-H sub 2 scattering

Elastic scattering of electrons by hydroge

Exact quantum mechanical reaction probabilities and rate constants for the isotopic collinear H+H2 reactions

Quantum mechanical calculations on three of the collinear H+H2 reactions involving D-substitutions are presented and compared with each other and with previous calculations on the H+H2 reaction itself. The energy at which the reaction probability becomes appreciable is well predicted by the vibrationally adiabatic model. The reaction probabilities at low energies (``tunneling'') are larger than predicted by tunneling through one-dimensional barriers for motion along the reaction coordinate. The deviations of the exact rates from transition state theory with unit transmission coefficient and with transmission coefficients corrected for tunneling and nonclassical reflection are examined. Transition state theory including tunneling is usually very accurate (correct within 20% for rate constants); but the errors are much larger at temperatures below 300°K. Although the main use of the present results is for testing approximate models of reaction, not for comparison with laboratory experiments, it is interesting to note that the isotope effects are in rough agreement with the (noncollinear) experimental ones. The results are used to examine the general validity of treatments of the dynamics which separate effects due to the different modes of motion

Reaction kinetics of muonium with the halogen gases (F2, Cl2, and Br2)

Copyright @ 1989 American Institute of PhysicsBimolecular rate constants for the thermal chemical reactions of muonium (Mu) with the halogen gases—Mu+X2→MuX+X—are reported over the temperature ranges from 500 down to 100, 160, and 200 K for X2=F2,Cl2, and Br2, respectively. The Arrhenius plots for both the chlorine and fluorine reactions show positive activation energies Ea over the whole temperature ranges studied, but which decrease to near zero at low temperature, indicative of the dominant role played by quantum tunneling of the ultralight muonium atom. In the case of Mu+F2, the bimolecular rate constant k(T) is essentially independent of temperature below 150 K, likely the first observation of Wigner threshold tunneling in gas phase (H atom) kinetics. A similar trend is seen in the Mu+Cl2 reaction. The Br2 data exhibit an apparent negative activation energy [Ea=(−0.095±0.020) kcal mol−1], constant over the temperature range of ∼200–400 K, but which decreases at higher temperatures, indicative of a highly attractive potential energy surface. This result is consistent with the energy dependence in the reactive cross section found some years ago in the atomic beam data of Hepburn et al. [J. Chem. Phys. 69, 4311 (1978)]. In comparing the present Mu data with the corresponding H atom kinetic data, it is found that Mu invariably reacts considerably faster than H at all temperatures, but particularly so at low temperatures in the cases of F2 and Cl2. The current transition state calculations of Steckler, Garrett, and Truhlar [Hyperfine Interact. 32, 779 (986)] for Mu+X2 account reasonably well for the rate constants for F2 and Cl2 near room temperature, but their calculated value for Mu+Br2 is much too high. Moreover, these calculations seemingly fail to account for the trend in the Mu+F2 and Mu+Cl2 data toward pronounced quantum tunneling at low temperatures. It is noted that the Mu kinetics provide a crucial test of the accuracy of transition state treatments of tunneling on these early barrier HX2 potential energy surfaces.NSERC (Canada), Donors of the Petroleum Research Fund, administered by the American Chemical Society, for their partial support of this research and the Canada Council

A Computational Procedure to Detect a New Type of High Dimensional Chaotic Saddle and its Application to the 3-D Hill's Problem

A computational procedure that allows the detection of a new type of high-dimensional chaotic saddle in Hamiltonian systems with three degrees of freedom is presented. The chaotic saddle is associated with a so-called normally hyperbolic invariant manifold (NHIM). The procedure allows to compute appropriate homoclinic orbits to the NHIM from which we can infer the existence a chaotic saddle. NHIMs control the phase space transport across an equilibrium point of saddle-centre-...-centre stability type, which is a fundamental mechanism for chemical reactions, capture and escape, scattering, and, more generally, ``transformation'' in many different areas of physics. Consequently, the presented methods and results are of broad interest. The procedure is illustrated for the spatial Hill's problem which is a well known model in celestial mechanics and which gained much interest e.g. in the study of the formation of binaries in the Kuiper belt.Comment: 12 pages, 6 figures, pdflatex, submitted to JPhys

First-response treatment after out-of-hospital cardiac arrest:a survey of current practices across 29 countries in Europe

Background: In Europe, survival rates after out-of-hospital cardiac arrest (OHCA) vary widely. Presence/absence and differences in implementation of systems dispatching First Responders (FR) in order to arrive before Emergency Medical Services (EMS) may contribute to this variation. A comprehensive overview of the different types of FR-systems used across Europe is lacking. Methods: A mixed-method survey and information retrieved from national resuscitation councils and national EMS services were used as a basis for an inventory. The survey was sent to 51 OHCA experts across 29 European countries. Results: Forty-seven (92%) OHCA experts from 29 countries responded to the survey. More than half of European countries had at least one region with a FR-system. Four categories of FR types were identified: (1) firefighters (professional/voluntary); (2) police officers; (3) citizen-responders; (4) others including off-duty EMS personnel (nurses, medical doctors), taxi drivers. Three main roles for FRs were identified: (a) complementary to EMS; (b) part of EMS; (c) instead of EMS. A wide variation in FR-systems was observed, both between and within countries. Conclusions: Policies relating to FRs are commonly implemented on a regional level, leading to a wide variation in FR-systems between and within countries. Future research should focus on identifying the FR-systems that most strongly influence survival. The large variation in local circumstances across regions suggests that it is unlikely that there will be a 'one-size fits all' FR-system for Europe, but examining the role of FRs in the Chain of Survival is likely to become an increasingly important aspect of OHCA research

Transition state geometry of driven chemical reactions on time-dependent double-well potentials

This paper was accepted for publication in the journal Physical Chemistry Chemical Physics and the definitive published version is available at http://dx.doi.org/10.1039/C6CP02519FReaction rates across time-dependent barriers are difficult to define and difficult to obtain using standard transition state theory approaches because of the complexity of the geometry of the dividing surface separating reactants and products. Using perturbation theory (PT) or Lagrangian descriptors (LDs), we can obtain the transition state trajectory and the associated recrossing-free dividing surface. With the latter, we are able to determine the exact reactant population decay and the corresponding rates to benchmark the PT and LD approaches. Specifically, accurate rates are obtained from a local description regarding only direct barrier crossings and to those obtained from a stability analysis of the transition state trajectory. We find that these benchmarks agree with the PT and LD approaches for obtaining recrossing-free dividing surfaces. This result holds not only for the local dynamics in the vicinity of the barrier top, but also for the global dynamics of particles that are quenched at the reactant or product wells after their sojourn over the barrier region. The double-well structure of the potential allows for long-time dynamics related to collisions with the outside walls that lead to long-time returns in the low-friction regime. This additional global dynamics introduces slow-decay pathways that do not result from the local transition across the recrossing-free dividing surface associated with the transition state trajectory, but can be addressed if that structure is augmented by the population transfer of the long-time returns

ANKRD54 preferentially selects Bruton's Tyrosine Kinase (BTK) from a Human Src-Homology 3 (SH3) domain library

Bruton's Tyrosine Kinase (BTK) is a cytoplasmic protein tyrosine kinase with a fundamental role in B-lymphocyte development and activation. The nucleocytoplasmic shuttling of BTK is specifically modulated by the Ankyrin Repeat Domain 54 (ANKRD54) protein and the interaction is known to be exclusively SH3-dependent. To identify the spectrum of the ANKRD54 SH3-interactome, we applied phage-display screening of a library containing all the 296 human SH3 domains. The BTK-SH3 domain was the prime interactor. Quantitative western blotting analysis demonstrated the accuracy of the screening procedure. Revealing the spectrum and specificity of ANKRD54-interactome is a critical step toward functional analysis in cells and tissues.Peer reviewe