Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations
Abstract Achieving control over chemical reaction’s rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize chemical and pharmaceutical industries. Strong light-matter interaction in optical or nanoplasmonic cavities might provide the knob to reach such control...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-38474-w |
| _version_ | 1797827419407646720 |
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| author | Fabijan Pavošević Robert L. Smith Angel Rubio |
| author_facet | Fabijan Pavošević Robert L. Smith Angel Rubio |
| author_sort | Fabijan Pavošević |
| collection | DOAJ |
| description | Abstract Achieving control over chemical reaction’s rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize chemical and pharmaceutical industries. Strong light-matter interaction in optical or nanoplasmonic cavities might provide the knob to reach such control. In this work, we demonstrate the catalytic and selectivity control of an optical cavity for two selected Diels-Alder cycloaddition reactions using the quantum electrodynamics coupled cluster (QED-CC) method. Herein, we find that by changing the molecular orientation with respect to the polarization of the cavity mode the reactions can be significantly inhibited or selectively enhanced to produce major endo or exo products on demand. This work highlights the potential of utilizing quantum vacuum fluctuations of an optical cavity to modulate the rate of Diels-Alder cycloaddition reactions and to achieve stereoselectivity in a practical and non-intrusive way. We expect that the present findings will be applicable to a larger set of relevant reactions, including the click chemical reactions. |
| first_indexed | 2024-04-09T12:47:59Z |
| format | Article |
| id | doaj.art-0c8a72cc0c24481fba549282412cbf51 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T12:47:59Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-0c8a72cc0c24481fba549282412cbf512023-05-14T11:21:24ZengNature PortfolioNature Communications2041-17232023-05-011411810.1038/s41467-023-38474-wComputational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuationsFabijan Pavošević0Robert L. Smith1Angel Rubio2Center for Computational Quantum Physics, Flatiron InstituteCenter for Computational Quantum Physics, Flatiron InstituteCenter for Computational Quantum Physics, Flatiron InstituteAbstract Achieving control over chemical reaction’s rate and stereoselectivity realizes one of the Holy Grails in chemistry that can revolutionize chemical and pharmaceutical industries. Strong light-matter interaction in optical or nanoplasmonic cavities might provide the knob to reach such control. In this work, we demonstrate the catalytic and selectivity control of an optical cavity for two selected Diels-Alder cycloaddition reactions using the quantum electrodynamics coupled cluster (QED-CC) method. Herein, we find that by changing the molecular orientation with respect to the polarization of the cavity mode the reactions can be significantly inhibited or selectively enhanced to produce major endo or exo products on demand. This work highlights the potential of utilizing quantum vacuum fluctuations of an optical cavity to modulate the rate of Diels-Alder cycloaddition reactions and to achieve stereoselectivity in a practical and non-intrusive way. We expect that the present findings will be applicable to a larger set of relevant reactions, including the click chemical reactions.https://doi.org/10.1038/s41467-023-38474-w |
| spellingShingle | Fabijan Pavošević Robert L. Smith Angel Rubio Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations Nature Communications |
| title | Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations |
| title_full | Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations |
| title_fullStr | Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations |
| title_full_unstemmed | Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations |
| title_short | Computational study on the catalytic control of e n d o/e x o Diels-Alder reactions by cavity quantum vacuum fluctuations |
| title_sort | computational study on the catalytic control of e n d o e x o diels alder reactions by cavity quantum vacuum fluctuations |
| url | https://doi.org/10.1038/s41467-023-38474-w |
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