Reaktionen von Molekülen in definierten Schwingungszuständen (III), die Reaktion von HCl(ν) mit H‐, D‐, Cl‐ und Br‐Atomen

Arnoldi, D.; Wolfrum, J.

doi:10.1002/bbpc.19760800914

Cited by 29 publications

(5 citation statements)

References 48 publications

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“…This would exactly reproduce our experimental rate constant at 298 K, although we have some reservations concerning the steep angular dependence of the TS energy barrier. It starts from a very low barrier at collinear TS geometry (Table of ref ). This function is remarkably different from those obtained with LEPS 33 or semiempirical ”diatomics-in-molecule” PES calculation .…”

Section: Discussionmentioning

confidence: 99%

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

Dobis

Benson

2000

J. Phys. Chem. A

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The bimolecular reaction H + Cl 2 f ΗCl + Cl (1) is studied in the very low-pressure reactor (VLPR) system at room temperature. Excellent mass balances are found between the Cl 2 consumption and both HCl as well as Cl product formation. This indicates that only reaction 1 occurs in the system. Its rate constant is k 1 ) (0.96 ( 0.04) × 10 -11 cm 3 /(molecule‚s) at 298 K. Two independent estimates of the A factor give a value log A 1 (298 K) ) -9.80 ( 0.15 (units of cm 3 /(molecule‚s)). Together with the measured rate constant this yields an activation energy of 1.7 ( 0.2 kcal/mol. All experimental data support a bent transition state for reaction 1.

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Section: Discussionmentioning

confidence: 99%

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

Dobis

Benson

2000

J. Phys. Chem. A

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“…Other experimental evidence establishes a lower bound of 7 kcal/mol for this barrier. 100 Several molecular beam studies 21,31,33 suggest that the exchange process occurs at about 9 kcal/mol but are unable to provide any more definitive insight into the barrier height. Clearly, further experimental and theoretical work is required to resolve the issue of the exchange barrier height and the competition between exchange and abstraction.…”

Section: Discussionmentioning

confidence: 99%

An Improved Potential Energy Surface for the H₂Cl System and Its Use for Calculations of Rate Coefficients and Kinetic Isotope Effects

et al. 1996

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We present a new potential energy surface (called G3) for the chemical reaction Cl + H2 → HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with least-action ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data. Disciplines Chemistry CommentsReprinted (adapted) ReceiVed: March 13, 1996; In Final Form: May 15, 1996 X We present a new potential energy surface (called G3) for the chemical reaction Cl + H 2 f HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with leastaction ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data.

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“…25 8.3 x 10-13 6.0 , 10-12 9.5 x 10-14 L 5 x 10-12 9.27 x 10-13 1.:) ;x 10-12 1. 6 x 10-12 7.B x 10-12 <5.1 )C 10-14 9.0 :x 1D-13 3.5 3.1 x 10-14 3.1 …”

Section: -13mentioning

confidence: 99%

“…These are quoted in multiples of 5%, following the prescription that errors of7, 8,9,10, and 11 % are listed as 10% and errors of12, 13,14,15, and 16% are listed as 15%, etc. Very small errors are listed as 1 %,2%,3%, etc.…”

Section: Error Quotationsmentioning

confidence: 99%

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Rate Coefficients for Vibrational Energy Transfer Involving the Hydrogen Halides

Leone

1982

Journal of Physical and Chemical Reference Data

105

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A comprehensive compilation of rate coefficients for vibration-to-vibratiun (V V) l:1ml vibration-to-translation (V -T) energy transfer processes involving hydrogen ha1ide molecules is presented. The literature has been surveyed from 1966 to July 1981. Rate coeffi-cient~ are grouped according to room temperature and low and high temperature results.Measured results are identified according to the type of process: V -V, V -T, or the sum of V -V and V -T processes. The method of measurement is identified along with the energy discrepancy, percent error, authors, and year of publication. The results are seen to be in excellent agreement when multiple measurements are available.The reference number, author, or first and last author, and date of the publication are given in the table. The complete citation is given in the bibliography at the end. Many groups have developed significant measurement skills and were frequently involved in many of the important measurements. The reader can quickly assess which values were obtained by each of several different groups without referring to the complete bibliography. Reliability of MethodsAs a technique, the laser fluorescence method has proven tu ue the most reliable and accurate. However, flow tube and double resonance methods also give excellent, accurate results. The methods with the greatest uncertainty appear to be laser gain, spectrophone, flash photolysis, shock tube studies and improperly done flow tube (flow reactor) measurements. Chemiluminescence depletion has typically only achieved relative rate coefficients. The combined methods, for example, laser fluorescence-discharge flow, are obviously more difficult technically, and thus have greater uncer-J.

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Reaktionen von Molekülen in definierten Schwingungszuständen (III), die Reaktion von HCl(ν) mit H‐, D‐, Cl‐ und Br‐Atomen

Cited by 29 publications

References 48 publications

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

An Improved Potential Energy Surface for the H₂Cl System and Its Use for Calculations of Rate Coefficients and Kinetic Isotope Effects

Rate Coefficients for Vibrational Energy Transfer Involving the Hydrogen Halides

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Reaktionen von Molekülen in definierten Schwingungszuständen (III), die Reaktion von HCl(ν) mit H‐, D‐, Cl‐ und Br‐Atomen

Cited by 29 publications

References 48 publications

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

Kinetic Study of the Reaction of Hydrogen Atoms with Molecular Chlorine at MilliTorr Pressures

An Improved Potential Energy Surface for the H2Cl System and Its Use for Calculations of Rate Coefficients and Kinetic Isotope Effects

Rate Coefficients for Vibrational Energy Transfer Involving the Hydrogen Halides

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An Improved Potential Energy Surface for the H₂Cl System and Its Use for Calculations of Rate Coefficients and Kinetic Isotope Effects