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Issue 6, 2016
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Photodissociation of acryloyl chloride at 193 nm: interpretation of the product energy distributions, and new elimination pathways

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Abstract

The ground electronic state potential energy surface of acryloyl chloride, CH2CHC(O)Cl, has been mapped using an automated transition state search procedure. A total of 174 minima, 527 TSs, and 20 different dissociation channels have been found. Among others, three novel HCl elimination pathways, namely, a five-center mechanism and two three-body dissociations (leading to CO + HCl + HCCH) have been discovered. While the bimodal character of the experimental HCl rotational distributions was previously attributed to the presence of two competing channels, our dynamics simulations show that a single channel, the four-center HCl elimination of CH2ClCHCO following a 1,3-Cl-shift of CH2CHC(O)Cl, displays a bimodal distribution in nearly prefect agreement with the experiment. Overall, our simulation results suggest that, as far as molecular elimination is concerned, this channel dominates in the 193 nm photodissociation of the molecule. The simulations also show evidence of non-IRC dynamics for this channel.

Graphical abstract: Photodissociation of acryloyl chloride at 193 nm: interpretation of the product energy distributions, and new elimination pathways

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The article was received on 15 Dec 2015, accepted on 14 Jan 2016 and first published on 19 Jan 2016


Article type: Paper
DOI: 10.1039/C5CP07759A
Citation: Phys. Chem. Chem. Phys., 2016,18, 5019-5026
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    Photodissociation of acryloyl chloride at 193 nm: interpretation of the product energy distributions, and new elimination pathways

    R. Pérez-Soto, S. A. Vázquez and E. Martínez-Núñez, Phys. Chem. Chem. Phys., 2016, 18, 5019
    DOI: 10.1039/C5CP07759A

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