Rates of H+CF3Br and Cl+NH3

Westenberg, A. A.; deHaas, N.

doi:10.1063/1.435082

Cited by 42 publications

(53 citation statements)

References 7 publications

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“…Room temperature determinations by Kumaran et al [745] (focused primarily on high temperature measurements) and Eberhard et al [428] (focused on obtaining yields of HCl product in different vibrational levels) are both in reasonable agreement with the recommendation as are the results from the relative rate studies by Su et al [1260] and by Rodebush and Klingelhoefer [1122]. The value for E/R is derived from a fit to the data at temperatures below 300 K reported by Westenberg and De Haas [1449], Lee et al [784], and…”

Section: -41supporting

confidence: 70%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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Section: -41supporting

confidence: 70%

Environmental effects of large igneous province magmatism: a Siberian perspective

Black

Lamarque

Shields

et al. 2015

Volcanism and Global Environmental Change

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“…These exchange reactions suggest an inverse dynamic isotope effect. The hydrogen analogue of the Mu + HCl reaction has been cited as an example for transition state theory in which a quasi-bound intermediate molecule is formed (56,57,58). In such a reaction intermediate, the zero point motion for the Mu-activated complex would be higher than the zero point motion for the analogous H complex giving rise to a larger activa tion energy.…”

Section: Muonium and Hydrogen In The Gas Phasementioning

confidence: 98%

Muonium Chemistry—A Review

Fleming

Garner

Vaz

et al. 1979

Advances in Chemistry

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The muonium atom can properly be regarded as an ultra light isotope of hydrogen, in which the proton nucleus is replaced by a positive muon of only one-ninth its mass. Within the Born-Oppenheimer approximation, the chemical identical up to differences in reaction dynamics; thus, mu onium chemistry studies greatly extend the range of observ able mass-sensitive effects in chemical kinetics. The theo retical background of muonium chemistry is presented and applied to thermal kinetic studies in both gas-and liquid -phase systems, drawing on current experimental results (primarily from TRIUMF and SIN) which reveal both nor mal and inverse dynamic isotope effects. Associated phe nomena such as muonium hot atom reactions are also dis cussed./chemical reactions of hydrogen atoms constitute some of the most ^ elementary processes in physical chemistry. The theory of the absolute rates of such reactions often has been clarified by measurements of isotope effects, differences in the reactions of the three naturally occurring isotopes of hydrogen: protium, deuterium, and tritium. The positronium (Ps) atom has been thought of as an ultralight isotope of hydrogen, but the analogy is poor, since chemical binding of Ps is a 'Present address:

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“…To the best of our knowledge, only two kinetics measurements have been reported experimentally. In 1977, using the flash photolysis resonance fluorescence technique, Westenberg and DeHass [23] determined the rate constant at room temperature, k(298 K) ¼ 1.23 Â 10 À13 cm molecule À1 s À1 . Recently, Gao et al [24], using the time-resolved resonance fluorescence technique, presented the first determination of the temperature dependence in the range 290-570 K for this endothermic reaction.…”

Section: Introductionmentioning

confidence: 99%

Analytical potential energy surface for the reaction with intermediate complexes NH₃ + Cl → NH₂ + HCl: Application to the kinetics study

Monge‐Palacios

Rangel

Corchado

et al. 2011

Int J of Quantum Chemistry

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We present for the first time an analytical potential energy surface (PES) for the reaction of hydrogen abstraction from ammonia by a chlorine atom. It has a very complicated shape with various maxima and minima. The functional form used in the development of the PES considered the stretching and bending nuclear motions, and the parameters in the calibration process were fitted to reproduce exclusively highlevel ab initio electronic structure calculations obtained at the CCSD(T) ¼ FULL/aug-ccpVTZ//CCSD(T) ¼ FC/cc-pVTZ single point level. Thus, the surface is completely symmetric with respect to the permutation of the three ammonia hydrogen atoms, and no experimental information is used in the process. The ab initio information used in the fit includes a wide spectrum of properties (equilibrium geometries, relative energies, and vibrational frequencies) of the reactants, products, saddle point, intermediate complexes in the entry and exit channels, points on the reaction path, and points on the reaction swath. By comparison with the reference results, we show that the resulting PES reproduces not only the ab initio data used in the fitting procedure but also other thermochemical and kinetics results computed at the same ab initio level, which were not used in the fit-equilibrium constants, rate constants, and kinetic isotope effects. This represents a severe test for the new surface. As a first application, we perform an extensive kinetics study using variational transition-state theory with semiclassical transmission coefficients over a wide temperature range, 200-2000 K, on this analytical PES. The forward rate constants reproduce the sparse experimental measurements, while the reverse ones reproduce the change of activation energy with temperature reported in another theoretical study, although unfortunately there are no experimental

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Rates of H+CF3Br and Cl+NH3

Cited by 42 publications

References 7 publications

Environmental effects of large igneous province magmatism: a Siberian perspective

Environmental effects of large igneous province magmatism: a Siberian perspective

Muonium Chemistry—A Review

Analytical potential energy surface for the reaction with intermediate complexes NH₃ + Cl → NH₂ + HCl: Application to the kinetics study

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Rates of H+CF3Br and Cl+NH3

Cited by 42 publications

References 7 publications

Environmental effects of large igneous province magmatism: a Siberian perspective

Environmental effects of large igneous province magmatism: a Siberian perspective

Muonium Chemistry—A Review

Analytical potential energy surface for the reaction with intermediate complexes NH3 + Cl → NH2 + HCl: Application to the kinetics study

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Analytical potential energy surface for the reaction with intermediate complexes NH₃ + Cl → NH₂ + HCl: Application to the kinetics study