A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I
Abstract The influence of quantum mechanics on the dynamics of chemical reactions is unknown for many processes in chemistry. Chemical reaction dynamics are often well described by quasiclassical motion of the atoms on quantum mechanical Born-Oppenheimer potential energy surfaces. Here we present a...
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Nature Portfolio
2025-03-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57086-0 |
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| author | Atilay Ayasli Arnab Khan Thomas Gstir Tim Michaelsen Dóra Papp Yan Wang Hongwei Song Minghui Yang Gábor Czakó Roland Wester |
| author_facet | Atilay Ayasli Arnab Khan Thomas Gstir Tim Michaelsen Dóra Papp Yan Wang Hongwei Song Minghui Yang Gábor Czakó Roland Wester |
| author_sort | Atilay Ayasli |
| collection | DOAJ |
| description | Abstract The influence of quantum mechanics on the dynamics of chemical reactions is unknown for many processes in chemistry. Chemical reaction dynamics are often well described by quasiclassical motion of the atoms on quantum mechanical Born-Oppenheimer potential energy surfaces. Here we present a dynamic isotope effect in a nucleophilic substitution reaction experiment that can only be explained by quasiclassical trajectory simulations for reactants containing deuterium atoms, but not when hydrogen atoms are involved. The calculated energy- and angle-differential cross sections are compared to experimental crossed-beam velocity map imaging data, which show significantly more forward scattering for hydrogenated compared to deuterated reactants. Quantum scattering calculations in reduced dimensions explain this by an increased reaction probability for large total angular momentum, a feature that is not captured in the quasiclassical approach. |
| format | Article |
| id | doaj-art-ba22b8704dbd4875ad39a068491d133b |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-ba22b8704dbd4875ad39a068491d133b2025-08-20T02:59:54ZengNature PortfolioNature Communications2041-17232025-03-0116111010.1038/s41467-025-57086-0A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3IAtilay Ayasli0Arnab Khan1Thomas Gstir2Tim Michaelsen3Dóra Papp4Yan Wang5Hongwei Song6Minghui Yang7Gábor Czakó8Roland Wester9Institut für Ionenphysik und Angewandte Physik, Universität InnsbruckInstitut für Ionenphysik und Angewandte Physik, Universität InnsbruckInstitut für Ionenphysik und Angewandte Physik, Universität InnsbruckInstitut für Ionenphysik und Angewandte Physik, Universität InnsbruckMTA-SZTE Lendület “Momentum” Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of SzegedSchool of Chemical and Environmental Engineering, Hubei Minzu UniversityKey Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of SciencesKey Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of SciencesMTA-SZTE Lendület “Momentum” Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of SzegedInstitut für Ionenphysik und Angewandte Physik, Universität InnsbruckAbstract The influence of quantum mechanics on the dynamics of chemical reactions is unknown for many processes in chemistry. Chemical reaction dynamics are often well described by quasiclassical motion of the atoms on quantum mechanical Born-Oppenheimer potential energy surfaces. Here we present a dynamic isotope effect in a nucleophilic substitution reaction experiment that can only be explained by quasiclassical trajectory simulations for reactants containing deuterium atoms, but not when hydrogen atoms are involved. The calculated energy- and angle-differential cross sections are compared to experimental crossed-beam velocity map imaging data, which show significantly more forward scattering for hydrogenated compared to deuterated reactants. Quantum scattering calculations in reduced dimensions explain this by an increased reaction probability for large total angular momentum, a feature that is not captured in the quasiclassical approach.https://doi.org/10.1038/s41467-025-57086-0 |
| spellingShingle | Atilay Ayasli Arnab Khan Thomas Gstir Tim Michaelsen Dóra Papp Yan Wang Hongwei Song Minghui Yang Gábor Czakó Roland Wester A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I Nature Communications |
| title | A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I |
| title_full | A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I |
| title_fullStr | A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I |
| title_full_unstemmed | A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I |
| title_short | A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I |
| title_sort | dynamic isotope effect in the nucleophilic substitution reaction between f and cd3i |
| url | https://doi.org/10.1038/s41467-025-57086-0 |
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