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Photochemical isomerization reactions of acrylonitrile. A mechanistic study

The mechanisms for the photochemical isomerization reactions are determined theoretically using the acrylonitrile model molecule. The CASSCF (twelve-electron/eleven-orbital active space) and MP2-CAS methods are respectively used with the 6-311G(d,p) and 6-311++G(3df,3pd) basis sets. The structure of...

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Autor principal: Su, Ming-Der
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9078173/
https://www.ncbi.nlm.nih.gov/pubmed/35539595
http://dx.doi.org/10.1039/c7ra12614j
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author Su, Ming-Der
author_facet Su, Ming-Der
author_sort Su, Ming-Der
collection PubMed
description The mechanisms for the photochemical isomerization reactions are determined theoretically using the acrylonitrile model molecule. The CASSCF (twelve-electron/eleven-orbital active space) and MP2-CAS methods are respectively used with the 6-311G(d,p) and 6-311++G(3df,3pd) basis sets. The structure of the conical intersection that plays a prominent role in the photoisomerization of acrylonitrile is obtained. The intermediates and the transition structures of the ground states are also calculated, to allow a qualitative explanation of the reaction pathways. These model studies suggest that the preferred reaction route is: acrylonitrile → Franck–Condon region → conical intersection → isoacrylonitrile → transition state → intermediate complex → transition state → cyanoacetylene. The theoretical evidence suggests that conical intersections found in this paper can give a better understanding of the photochemical reactions of acrylonitrile and support the experimental observations.
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spelling pubmed-90781732022-05-09 Photochemical isomerization reactions of acrylonitrile. A mechanistic study Su, Ming-Der RSC Adv Chemistry The mechanisms for the photochemical isomerization reactions are determined theoretically using the acrylonitrile model molecule. The CASSCF (twelve-electron/eleven-orbital active space) and MP2-CAS methods are respectively used with the 6-311G(d,p) and 6-311++G(3df,3pd) basis sets. The structure of the conical intersection that plays a prominent role in the photoisomerization of acrylonitrile is obtained. The intermediates and the transition structures of the ground states are also calculated, to allow a qualitative explanation of the reaction pathways. These model studies suggest that the preferred reaction route is: acrylonitrile → Franck–Condon region → conical intersection → isoacrylonitrile → transition state → intermediate complex → transition state → cyanoacetylene. The theoretical evidence suggests that conical intersections found in this paper can give a better understanding of the photochemical reactions of acrylonitrile and support the experimental observations. The Royal Society of Chemistry 2018-02-02 /pmc/articles/PMC9078173/ /pubmed/35539595 http://dx.doi.org/10.1039/c7ra12614j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Su, Ming-Der
Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title_full Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title_fullStr Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title_full_unstemmed Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title_short Photochemical isomerization reactions of acrylonitrile. A mechanistic study
title_sort photochemical isomerization reactions of acrylonitrile. a mechanistic study
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9078173/
https://www.ncbi.nlm.nih.gov/pubmed/35539595
http://dx.doi.org/10.1039/c7ra12614j
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