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

Physical Chemistry Chemical Physics : PCCP
Raúl Pérez-SotoEmilio Martínez-Núñez

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.

References

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Nov 11, 2009·The Journal of Physical Chemistry. a·Weiqiang WuHongmei Su
Jan 26, 2011·The Journal of Physical Chemistry. a·Zahra HomayoonEmilio Martínez-Núñez
Sep 21, 2011·Physical Review Letters·Fabio Pietrucci, Wanda Andreoni
Jan 10, 2014·Journal of Computational Chemistry·Otávio Beruski, Luciano N Vidal
Nov 22, 2014·Journal of Computational Chemistry·Emilio Martínez-Núñez
Feb 14, 2015·Physical Chemistry Chemical Physics : PCCP·Saulo A Vázquez, Emilio Martínez-Núñez
May 20, 2015·Physical Chemistry Chemical Physics : PCCP·Emilio Martínez-Núñez

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Citations

Sep 25, 2018·Journal of Computational Chemistry·Aurelio RodríguezEmilio Martínez-Núñez
Dec 6, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Saulo A VázquezEmilio Martinez-Nunez
Apr 6, 2021·The Journal of Physical Chemistry. a·Christian T MatthaeiIngo Fischer
Jul 28, 2021·Physical Chemistry Chemical Physics : PCCP·Zhuang WuXiaoqing Zeng
Aug 14, 2021·Journal of Computational Chemistry·Emilio Martínez-NúñezSaulo A Vazquez

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