Home Physical Sciences Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO
Article
Licensed
Unlicensed Requires Authentication

Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO

  • Zahra Homayoon , Joel M. Bowman EMAIL logo , Arghya Dey , Chamara Abeysekera , Ravin Fernando and Arthur G. Suits EMAIL logo
Published/Copyright: July 8, 2013
Zeitschrift für Physikalische Chemie
From the journal Zeitschrift für Physikalische Chemie Volume 227 Issue 11

Abstract

Characteristic signatures of roaming are seen in the translational energy distribution and rotational energy distributions in the products CH3O + NO from the unimolecular dissociation of nitromethane in both theory and experiment. Calculations on a new global potential energy surface reveal the detailed roaming-isomerization dynamics in this process, and these are supported by the experimental observations. Calculations find a characteristic of roaming, namely production of vibrationally excited CH3O, which is consistent with experiment. This continues to challenge the conventional idea in transition state theory of a localized transition state bottleneck that is a cornerstone of chemical reaction theory.

Keywords: Roaming Reaction; Photochemistry; Theoretical Dynamics; Trajectory Calculations; Potential Energy Surfaces; Isomerization
Received: 2013-3-5
Published Online: 2013-7-8
Published in Print: 2013-11-1

© 2013 by Walter de Gruyter Berlin Boston

Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Editorial
  4. Milestones in Physical Chemistry (I) – A Special Issue Honoring the Seminal Work of Henry Eyring and Michael Polanyi
  5. International Collaborations are nothing new... and sometimes they are simply amazing
  6. Personal Perspective
  7. A Comment on Henry Eyring
  8. Comment
  9. Michael Polanyi, the Scientist
  10. Historical Paper
  11. On Simple Gas Reactions
  12. Feature Article
  13. Probing Quantum Dynamics of Elementary Chemical Reactions via Accurate Potential Energy Surfaces
  14. Elementary Gas Phase Reactions
  15. Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO
  16. Simultaneous Measurement of Reactive and Inelastic Scattering: Differential Cross Section of the H + HD → HD(v′, j′) + H Reaction
  17. The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst
  18. A Theoretical Study of the X-Abstraction Reactions (X = H, Br, or I) from CH2IBr by OH Radicals: Implications for Atmospheric Chemistry
  19. Models for Intrinsic Non-RRKM Dynamics. Decomposition of the SN2 Intermediate Cl––CH3Br
  20. Chemical Reactions at Surfaces
  21. Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison
  22. 7D Quantum Dynamics of H2 Scattering from Cu(111): The Accuracy of the Phonon Sudden Approximationy
  23. Exploring Pathways of Photoaddition Reactions by Artificial Force Induced Reaction Method: A Case Study on the Paternò–Büchi Reaction
  24. Kinetic Prefactors of Reactions on Solid Surfaces
  25. Electron-Transfer-Induced Dissociation of H2 on Gold Nanoparticles: Excited-State Potential Energy Surfaces via Embedded Correlated Wavefunction Theory
  26. Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface
  27. Initial Sticking Coefficient of H2 on the Pd–Cu(111) Surface Alloy at very Low Coverages
  28. Catalyzed Surface-Aligned Reaction, H(ad) + H2(ad) = H2(g) + H(ad) on Coinage Metals
  29. Nitrogen Scattering at Ru(0001) Surfaces
  30. Ready, Set and no Action: A Static Perspective on Potential Energy Surfaces commonly used in Gas-Surface Dynamics
  31. Reactions in Clusters
  32. Potential Energy Surfaces and Rates of Spin Transitions
  33. A Full-Dimensional Neural Network Potential-Energy Surface for Water Clusters up to the Hexamer
  34. Embedded Cluster Models for Reactivity of the Hydrated Electron
  35. Novel Experimenta Methods
  36. Stark Deceleration of NO Radicals
  37. A Forty-Segment Molecular Synchrotron
https://doi.org/10.1524/zpch.2013.0409
Keywords for this article
Roaming Reaction; Photochemistry; Theoretical Dynamics; Trajectory Calculations; Potential Energy Surfaces; Isomerization

Articles in the same Issue

  1. Masthead
  2. Masthead
  3. Editorial
  4. Milestones in Physical Chemistry (I) – A Special Issue Honoring the Seminal Work of Henry Eyring and Michael Polanyi
  5. International Collaborations are nothing new... and sometimes they are simply amazing
  6. Personal Perspective
  7. A Comment on Henry Eyring
  8. Comment
  9. Michael Polanyi, the Scientist
  10. Historical Paper
  11. On Simple Gas Reactions
  12. Feature Article
  13. Probing Quantum Dynamics of Elementary Chemical Reactions via Accurate Potential Energy Surfaces
  14. Elementary Gas Phase Reactions
  15. Experimental and Theoretical Studies of Roaming Dynamics in the Unimolecular Dissociation of CH3NO2 to CH3O + NO
  16. Simultaneous Measurement of Reactive and Inelastic Scattering: Differential Cross Section of the H + HD → HD(v′, j′) + H Reaction
  17. The Decomposition of Hydrazine in the Gas Phase and over an Iridium Catalyst
  18. A Theoretical Study of the X-Abstraction Reactions (X = H, Br, or I) from CH2IBr by OH Radicals: Implications for Atmospheric Chemistry
  19. Models for Intrinsic Non-RRKM Dynamics. Decomposition of the SN2 Intermediate Cl––CH3Br
  20. Chemical Reactions at Surfaces
  21. Electronic Excitations in the Course of the Reaction of H with Coinage and Noble Metal Surfaces: A Comparison
  22. 7D Quantum Dynamics of H2 Scattering from Cu(111): The Accuracy of the Phonon Sudden Approximationy
  23. Exploring Pathways of Photoaddition Reactions by Artificial Force Induced Reaction Method: A Case Study on the Paternò–Büchi Reaction
  24. Kinetic Prefactors of Reactions on Solid Surfaces
  25. Electron-Transfer-Induced Dissociation of H2 on Gold Nanoparticles: Excited-State Potential Energy Surfaces via Embedded Correlated Wavefunction Theory
  26. Toward Detection of Electron-Hole Pair Excitation in H-atom Collisions with Au(111): Adiabatic Molecular Dynamics with a Semi-Empirical Full-Dimensional Potential Energy Surface
  27. Initial Sticking Coefficient of H2 on the Pd–Cu(111) Surface Alloy at very Low Coverages
  28. Catalyzed Surface-Aligned Reaction, H(ad) + H2(ad) = H2(g) + H(ad) on Coinage Metals
  29. Nitrogen Scattering at Ru(0001) Surfaces
  30. Ready, Set and no Action: A Static Perspective on Potential Energy Surfaces commonly used in Gas-Surface Dynamics
  31. Reactions in Clusters
  32. Potential Energy Surfaces and Rates of Spin Transitions
  33. A Full-Dimensional Neural Network Potential-Energy Surface for Water Clusters up to the Hexamer
  34. Embedded Cluster Models for Reactivity of the Hydrated Electron
  35. Novel Experimenta Methods
  36. Stark Deceleration of NO Radicals
  37. A Forty-Segment Molecular Synchrotron
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Winner of the OpenAthens UX Award 2026
Winner of the OpenAthens UX Award 2026
Have an idea on how to improve our website?
Please write us.
© 2026 De Gruyter Brill
Downloaded on 13.3.2026 from https://www.degruyterbrill.com/document/doi/10.1524/zpch.2013.0409/html
Scroll to top button