Search results for "React"
showing 10 items of 9101 documents
Nanoscale Etching of GaAs and InP in Acidic H<sub>2</sub>O<sub>2</sub> Solution: A Striking Contrast in Kinetics and Surface …
2018
In this study of nanoscale etching for state-of-the-art device technology the importance of the nature of the surface oxide, is demonstrated for two III-V materials. Etching kinetics for GaAs and InP in acidic solutions of hydrogen peroxide are strikingly different. GaAs etches much faster, while the dependence of the etch rate on the H+ concentration differs markedly for the two semiconductors. Surface analysis techniques provided information on the surface composition after etching: strongly non-stoichiometric porous (hydr)oxides on GaAs and a thin stoichiometric oxide that forms a blocking layer on InP. Reaction schemes are provided that allow one to understand the results, in particular…
Aqueous Corrosion of the GeSe4 Chalcogenide Glass: Surface Properties and Corrosion Mechanism
2009
International audience; The aqueous corrosion behavior of the GeSe4 glass composition has been studied over time under various conditions (temperature and pH). The evolution of the surface topography by atomic force microscopy and properties such as surface hardness and reduced modulus, as well as the optical transmission in the 1-16 μm window, have been measured as a function of time spent in the corrosive solution. It was found that even if the glass reacts at room temperature, its optical transparency was barely affected. Nevertheless, the durability of GeSe4 was found to be drastically affected by an increase of both temperature and pH. Furthermore, pure selenium nanoparticles were form…
Unexpected Substituent Effects in the Iso-Heterocyclic Boulton-Katritzky Rearrangement of 3-Aroylamino-5-methyl-1,2,4-oxadiazoles: A Mechanistic Stud…
2019
The kinetics of the iso-heterocyclic mononuclear rearrangement of some 3-aroylamino-5-methyl-1,2,4-ozadiazoles was carefully examined under largely variable acidic or alkaline conditions. This reaction may proceed via two different mechanistic pathways (an uncatalyzed and a base-catalyzed one), as accounted for also by the evaluation of the relevant activation parameters. Substituent effects, as quantified by means of the Hammett’s equation, appear relatively modest; however, they reveal some interesting anomalies, which enabled us to draw a very precise picture of the intimate reaction course.
Origin of Enzymatic Kinetic Isotope Effects in Human Purine Nucleoside Phosphorylase
2017
Here we report a study of the effect of heavy isotope labeling on the reaction catalyzed by human purine nucleoside phosphorylase (hPNP) to elucidate the origin of its catalytic effect and of the enzymatic kinetic isotope effect (EKIE). Using quantum mechanical and molecular mechanical (QM/MM) molecular dynamics (MD) simulations, we study the mechanism of the hPNP enzyme and the dynamic effects by means of the calculation of the recrossing transmission coefficient. A free energy surface (FES), as a function of both a chemical and an environmental coordinate, is obtained to show the role of the environment on the chemical reaction. Analysis of reactive and nonreactive trajectories allows us …
Quantum dynamics of 16O in collision with ortho- and para-17O17O
2017
Abstract We report full quantum dynamical observables, such as integral and differential cross sections and rate constants, for the 16 O + 17 O 17 O reactive collision process. We particularly emphasize the effect coming from the nonzero nuclear spin of 17 O, leading to two nuclear spin isomers of 34 O 2 , ortho- and para- 34 O 2 which can be studied independently and behave differently. A comparison with the 16 O + 18 O 18 O collision is given. We find that processes involving 17 O 17 O are always faster than with 18 O 18 O.
Adaptive Finite Temperature String Method in Collective Variables.
2017
Here we present a modified version of the on-the-fly string method for the localization of the minimum free energy path in a space of arbitrary collective variables. In the proposed approach the shape of the biasing potential is controlled by only two force constants, defining the width of the potential along the string and orthogonal to it. The force constants and the distribution of the string nodes are optimized during the simulation, improving the convergence. The optimized parameters can be used for umbrella sampling with a path CV along the converged string as the reaction coordinate. We test the new method with three fundamentally different processes: chloride attack to chloromethane…
Unravelling the kinetics and molecular mechanism of the degenerate Cope rearrangement of bullvalene
2020
The kinetics and molecular mechanism of the gas phase degenerate Cope rearrangement (DCR) of bullvalene have been investigated by applying quantum mechanical calculations. Highly accurate energies (CBS-QB3 and CBS-APNO) and RRKM calculations were employed to study the kinetics and ‘fall-off’ behavior. It was found that the DCR of bullvalene (C3v) occurs through a bishomoaromatic transition structure (C2v) with an energy barrier of ∼49 kJ mol−1. The calculated activation energy and enthalpy were in good agreement with the available values in the literature, but lower than those of common Cope rearrangement; this result is related to the high stabilization energy due to the interaction of the…
Gas-Phase Synthesis of the Elusive Trisilicontetrahydride Species (Si3H4)
2016
The bimolecular gas-phase reaction of ground-state atomic silicon (Si; 3P) with disilane (Si2H6; 1A1g) was explored under single-collision conditions in a crossed molecular beam machine at a collision energy of 21 kJ mol–1. Combined with electronic structure calculations, the results suggest the formation of Si3H4 isomer(s) along with molecular hydrogen via indirect scattering dynamics through Si3H6 collision complex(es) and intersystem crossing from the triplet to the singlet surface. The nonadiabatic reaction dynamics can synthesize the energetically accessible singlet Si3H4 isomers in overall exoergic reaction(s) (−93 ± 21 kJ mol–1). All reasonable reaction products are either cyclic or …
Quantum Dynamics of the 17O + 32O2 Collision Process
2016
We report full quantum integral and differential cross sections and rate constants for the 17O + 32O2 reactive process. This constitutes the first quantum scattering study of the 17O16O16O system. We emphasize the comparison with the 18O + 32O2 collision in close connection to the mass-independent fractionation (hereafter referred to as MIF) puzzle for ozone in atmospheric chemistry. We find similar general trends in the cross sections and rate constants for both rare isotopes, but we note some singular behaviors peculiar to the use of 17O isotope, particularly at the lowest collision energies.
The research reactor TRIGA Mainz – a strong and versatile neutron source for science and education
2019
Abstract The TRIGA Mark II-reactor at the Johannes Gutenberg University Mainz (JGU) is one of three research reactors in Germany. The TRIGA Mainz became first critical on August 3rd, 1965. It can be operated in the steady state mode with a maximum power of 100 kWth and in the pulse mode with a peak power of 250 MWth and a pulse length of 30 ms. The TRIGA Mainz is equipped with a central thimble, a rotary specimen rack, three pneumatic transfer systems, four beam tubes, and a graphite thermal column. The TRIGA Mainz is intensively used both for basic and applied research in nuclear chemistry and nuclear physics. Two sources for ultra-cold neutrons (UCN) are operational at two beam ports. At …