| DOI | Resolve DOI: https://doi.org/10.1016/j.chemphys.2018.09.012 |
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| Author | Search for: Macdonell, Ryan J.; Search for: Schuurman, Michael S.1 |
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| Affiliation | - National Research Council of Canada. Security and Disruptive Technologies
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| Format | Text, Article |
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| Abstract | The energetic and structural trends in the minimum energy conical intersections of a series of substituted ethylenes are explained by the degree to which the chemical substituents polarize electron density across the C=C double bond. The addition of a substituent that significantly polarizes the electron density also reduces the magnitude of the large-amplitude pyramidalization motions required to reach a conical intersection and can thus very effectively “direct” these motions to occur at a specific carbon atom. These observations are summarized via the construction of a reduced dimensionality representation of the relevant potential energy surfaces inspired by a previously reported 3-state model for biradical systems. On-the-fly nonadiabatic dynamics simulations reveal that this effect dictates the dominant excited state decay pathway for acrylonitrile (π-acceptor CN substituent) and vinylamine (π-donor NH2 substituent). The ab initio multiple spawning simulations show that population transfer to the ground electronic state for both molecules occurs primarily in the regions around the substituent-altered minimum energy conical intersections, demonstrating that chemical substitution may be used to selectively alter photochemical pathways. |
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| Publication date | 2018-09-14 |
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| Publisher | Elsevier |
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| In | |
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| Note | Erratum published in volume 532, 1 April 2020, 110698. DOI: 10.1016/j.chemphys.2020.110698 |
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| Language | English |
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| Peer reviewed | Yes |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | 8a866387-79e6-4cac-b7e9-35591e4d8a23 |
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| Record created | 2020-06-23 |
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| Record modified | 2020-06-29 |
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