MRCISD studies of the dissociation of vinylhydroperoxide, CH2CHOOH: there is a saddle point
Related Experiment Video
Updated: May 22, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
1Laboratory of Physical Chemistry, University of Helsinki, P.O. BOX 55, Helsinki FI-00014, Finland. theo.kurten@helsinki.fi
Abstract:
Multireference ab initio methods are used to investigate the dissociation of vinylhydroperoxide CH(2)CHOOH into vinyl oxide and hydroxide radicals. In contrast to some previous studies, which claim the reaction has no saddle point, our calculations confirm that the dissociation is associated with a kinetic barrier (transition state). We further propose the existence of a hitherto undiscovered radical-radical complex on the reaction path. The computed reaction energetics are used to estimate VHP dissociation rates, and the results are discussed in the context of atmospheric ozonolysis pathways. Qualitative aspects of the dissociation of larger, substituted vinylhydroperoxides are also discussed.
Related Concept Videos
Regioselectivity of Electrophilic Additions-Peroxide Effect
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
Mass Spectrometry: Molecular Fragmentation Overview
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...

