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Roaming in acetaldehyde.

Vladimír Krajňák1, Stephen Wiggins1,2

  • 1School of Mathematics, University of Bristol, Fry Building, Woodland Road, Bristol BS8 1UG, United Kingdom.

The Journal of Chemical Physics
|June 24, 2024
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Summary
This summary is machine-generated.

Acetaldehyde photodissociation shows two roaming pathways, unlike formaldehyde. Shorter-range roaming is unique to acetaldehyde, driven by repulsive forces not seen in simpler models.

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Area of Science:

  • Chemical Dynamics
  • Photochemistry
  • Molecular Spectroscopy

Background:

  • Roaming dynamics in molecular photodissociation are crucial for understanding reaction pathways.
  • Acetaldehyde (CH3CHO) and formaldehyde (H2CO) exhibit distinct photochemical behaviors.

Purpose of the Study:

  • To investigate and differentiate roaming dynamics in acetaldehyde photodissociation.
  • To compare acetaldehyde's roaming mechanisms with those of formaldehyde.

Main Methods:

  • Full-dimensional trajectory studies on acetaldehyde.
  • Analysis using a two-degree-of-freedom restricted model.
  • Phase space analysis to assess pathway accessibility.

Main Results:

  • Evidence for two distinct roaming pathways in acetaldehyde photodissociation.
  • Roaming observed at shorter (9-11.5 au) and larger (14.5-22.9 au) CH3-HCO separations.
  • Shorter-range roaming is unique to acetaldehyde, involving repulsive interactions.

Conclusions:

  • Acetaldehyde exhibits multiple roaming mechanisms, contributing to its increased roaming propensity.
  • A restricted model accurately reproduces longer-range roaming, analogous to formaldehyde.
  • Shorter-range roaming in acetaldehyde is facilitated by factors absent in simplified models.