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Towards Simplified Thermal and Specific Rigidity Factors for Ion-Molecule Reactions and Ion Fragmentations

Published/Copyright: September 25, 2009
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 223 Issue 4-5

Abstract

Rate constants for capture-controlled ion-molecule reactions and ion fragmentations are analyzed. It is shown that exothermic ion-molecule reactions governed by long-range potentials (class I reactions) and ion fragmentations and the reverse ion-molecule associations with large contributions from valence potentials (class II reactions) require different treatments. The results are expressed by phase space theory and rigidity factors accounting for the anisotropy of the potentials. Thermal and specific rigidity factors, frigid(T) and frigid(E,J)respectively, need to be internally consistent. Simplified two-parameter expressions for the two rigidity factors are designed with the hope that fitting of the parameters to limited experimental data allows one to extrapolate to unexplored ranges of conditions.

Keywords: Fragmentation of Molecular Ions; Specific Rate Constants; Rigidity Factors
* Correspondence address: Universität Göttingen, Institut für Physikalische Chemie, Tammannstraße 6, 37077 Göttingen, Deutschland,
Published Online: 2009-9-25
Published in Print: 2009-5-1

© by Oldenbourg Wissenschaftsverlag, München, Germany

Articles in the same Issue

  1. Preface
  2. Towards Simplified Thermal and Specific Rigidity Factors for Ion-Molecule Reactions and Ion Fragmentations
  3. Chemistry and Microphysics of Atmospheric Aerosol Surfaces: Laboratory Techniques and Applications
  4. The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study
  5. CH2Cl and CHCl2 Radical Chemistry: The Formation by the Reactions CH3Cl + F and CH2Cl2 + F and The Destruction by the Reactions CH2Cl + O and CHCl2 + O
  6. Formation of H-atoms in the Pyrolysis of 1,3-butadiene and 2-butyne: A Shock Tube and Modelling Study
  7. High-level Ab-initio Calculations for Astrochemically Relevant Polyynes (HC2nH), their Isomers (C2nH2) and their Anions (C2nH−)
  8. Investigation of the Hierarchical Structure of Kinetic Models in Ignition Problems
  9. Laser Diagnostics for the Model Development in Turbulent Premixed Flames
  10. Sampling Probe Influences on Temperature and Species Concentrations in Molecular Beam Mass Spectroscopic Investigations of Flat Premixed Low-pressure Flames
  11. Shock-Tube Study of the Reactions of Hydrogen Atoms with Benzene and Phenyl Radicals
  12. The Generation of a Compact n-Heptane / Toluene Reaction Mechanism Using the Chemistry Guided Reduction (CGR) Technique
  13. Modeling of Rich Premixed C2H4/O2/Ar and C2H4/Dimethoxymethane/O2/Ar Flames
  14. Conformation and Aggregation of Proline Esters and Their Aromatic Homologs: Pyramidal vs. Planar RR´N-H in Hydrogen Bonds
  15. A Two-equation Model to Simulate Soot Formation under Shock-tube Conditions
  16. CO Formation in the 254 nm Gas Phase Photolysis of Nitrosobenzene-Oxygen Mixtures at Room Temperature
  17. Experimental and Numerical Investigation of Fe(CO)5 Addition to a Laminar Premixed Hydrogen/Oxygen/Argon Flame
  18. Structures of Laminar Methane/Nitrogen/Oxygen, Methane/Oxygen and Methane/Liquid Oxygen Counterflow Flames for Cryogenic Conditions and Elevated Pressures
https://doi.org/10.1524/zpch.2009.6035
Keywords for this article
Fragmentation of Molecular Ions; Specific Rate Constants; Rigidity Factors

Articles in the same Issue

  1. Preface
  2. Towards Simplified Thermal and Specific Rigidity Factors for Ion-Molecule Reactions and Ion Fragmentations
  3. Chemistry and Microphysics of Atmospheric Aerosol Surfaces: Laboratory Techniques and Applications
  4. The Products of the Reactions of o-Benzyne with Ethene, Propene, and Acetylene: A Combined Mass Spectrometric and Quantum Chemical Study
  5. CH2Cl and CHCl2 Radical Chemistry: The Formation by the Reactions CH3Cl + F and CH2Cl2 + F and The Destruction by the Reactions CH2Cl + O and CHCl2 + O
  6. Formation of H-atoms in the Pyrolysis of 1,3-butadiene and 2-butyne: A Shock Tube and Modelling Study
  7. High-level Ab-initio Calculations for Astrochemically Relevant Polyynes (HC2nH), their Isomers (C2nH2) and their Anions (C2nH−)
  8. Investigation of the Hierarchical Structure of Kinetic Models in Ignition Problems
  9. Laser Diagnostics for the Model Development in Turbulent Premixed Flames
  10. Sampling Probe Influences on Temperature and Species Concentrations in Molecular Beam Mass Spectroscopic Investigations of Flat Premixed Low-pressure Flames
  11. Shock-Tube Study of the Reactions of Hydrogen Atoms with Benzene and Phenyl Radicals
  12. The Generation of a Compact n-Heptane / Toluene Reaction Mechanism Using the Chemistry Guided Reduction (CGR) Technique
  13. Modeling of Rich Premixed C2H4/O2/Ar and C2H4/Dimethoxymethane/O2/Ar Flames
  14. Conformation and Aggregation of Proline Esters and Their Aromatic Homologs: Pyramidal vs. Planar RR´N-H in Hydrogen Bonds
  15. A Two-equation Model to Simulate Soot Formation under Shock-tube Conditions
  16. CO Formation in the 254 nm Gas Phase Photolysis of Nitrosobenzene-Oxygen Mixtures at Room Temperature
  17. Experimental and Numerical Investigation of Fe(CO)5 Addition to a Laminar Premixed Hydrogen/Oxygen/Argon Flame
  18. Structures of Laminar Methane/Nitrogen/Oxygen, Methane/Oxygen and Methane/Liquid Oxygen Counterflow Flames for Cryogenic Conditions and Elevated Pressures
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