State-to-state differential cross sections for a four-atom reaction: H2 + OH → H2O + H in full dimensions
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The time-dependent wave packet method has been employed to calculate state-to-state differential cross sections for the title reaction in full dimensions. It is found that the majority of H2O is produced in the first stretching excited states, with a large fraction of available energy for the reaction ending up as product internal motion. The differential cross sections for collision energy up to 0.4 eV are all peaked in the backward direction, but the width of the angular distribution increases considerably as the increase of collision energy. The isotope effect was also examined by comparing the scattering angular distribution for the title reaction with those for the HD + OH and D2 + OH reactions obtained in our previous work.Keywords:
Kinetic isotope effect
Reaction dynamics
Abstract Secondary α-deuterium isotope effects were studied in the symmetrical nucleophilic substitution of the substituted chloromethanes in acetonitrile. The apparent second order rate coefficients show a significant isotope effect for chloromethyl aryl ethers and sulfides (1.11–1.14 per D), and an intermediate value of 1.05 for cinnamyl chlorides. 2-Arylethyl chlorides were shown to give an appreciable isotope effect of 1.03–1.04, and arylchloromethanes to give varying amount of the isotope effect from 1.006 to 1.050 depending upon the ring substituent. The deuterium label also gave rise to a significant equilibrium isotope effect on the substrate-nucleophile association in the reaction mixture. The observation of an equilibrium isotope effect suggested a possibility that an apparent isotope effect was a composite of the thermodynamic and the kinetic isotope effects. Thus the dissection resulted in a uniform and a fairly large kinetic isotope effect for all the activated substrates studied and in a small kinetic isotope effect for 2-arylethyl chloride. The results are explained in a framework of loose–tight transition state.
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Kinetic isotope effect
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For two atoms whose ionization potentials are considerably different, an exact asymptotic expression for the exchange interaction is derived. This interaction is connected with the energy level shift of an excited atom, colliding with a ground state atom. From the general expression for this quantity the results of Smirnov and Ovchinikova are obtained as special cases.
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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSecondary deuterium isotope effects for certain acyl transfer reactions of phenyl formatesLuciano Do Amaral, Marilene P. Bastos, Herbert G. Bull, Juan J. Oritz, and E CordesCite this: J. Am. Chem. Soc. 1979, 101, 1, 169–173Publication Date (Print):January 1, 1979Publication History Published online1 May 2002Published inissue 1 January 1979https://pubs.acs.org/doi/10.1021/ja00495a028https://doi.org/10.1021/ja00495a028research-articleACS PublicationsRequest reuse permissionsArticle Views45Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
Kinetic isotope effect
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Deuterium isotope dependence on the excited-state intramolecular proton transfer rate and nuclear wave packet motions was investigated by time-resolved fluorescence. High time resolution reveals the role of OH stretching motion on the proton transfer reaction.
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The state-resolved isotope effect on the cross sections of 2p atom formation via precursor doubly excited states of and is obtained at 80 eV incident electron energy and scattering angle by means of coincident electron-energy-loss spectroscopy as well as theoretical fits based on the reflection approximation and the survival probability. It turns out that the degree of the isotope effect depends strongly on the precursor doubly excited states and hence is a significant character of them. The origin of this dependence is discussed.
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Kinetic isotope effect
Nucleophilic Addition
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The semirigid vibrating rotor target model is applied to study the isotope effect in reaction H+CH4→H2+CH3 using time-dependent wave-packet method. The reaction probabilities for producing H2 and HD product channels are calculated. The energy dependence of the reaction probabilities shows oscillating structures for both reaction channels. At low temperature or collision energies, the H atom abstraction is favored due to tunnelling effect. In partially deuterated CHxDy (x+y=4), the breaking of the C–H bond is favored over that of the C–D bond in the entire energy range studied. In H+CHD3 reaction at high energies, the HD product dominates simply due to statistical factor.
Kinetic isotope effect
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Chain reaction
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Balmer series
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Elimination reaction
Kinetic isotope effect
Sodium ethoxide
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