A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I
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.
Authors
- Thomas Gstir (ORCID: https://orcid.org/0009-0000-8290-4676)
- Dóra Papp (ORCID: https://orcid.org/0000-0003-1951-7619)
- Atilay Ayasli
- Hongwei Song (ORCID: https://orcid.org/0000-0001-8401-2364)
- Tim Michaelsen (ORCID: https://orcid.org/0000-0002-5937-7393)
- Roland Wester (ORCID: https://orcid.org/0000-0001-7935-6066)
- Gábor Czakó (ORCID: https://orcid.org/0000-0001-5136-4777)
- Minghui Yang (ORCID: https://orcid.org/0000-0003-1067-2217)
- Arnab Khan (ORCID: https://orcid.org/0000-0002-1343-8031)
- Yan Wang (ORCID: https://orcid.org/0000-0002-8648-2172)
Institutions
- Minzu University of China (CN)
- Universität Innsbruck (AT)
- Chinese Academy of Sciences (CN)
- University of Szeged (HU)
- Indian Institute of Science Education and Research, Bhopal (IN)
- Wuhan Institute of Physics and Mathematics (CN)
- Wuhan National Laboratory for Optoelectronics (CN)
- Huazhong University of Science and Technology (CN)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-03-08
- DOI
- https://doi.org/10.1038/s41467-025-57086-0
- Citations
- 4
- Primary Topic
- Fluorine in Organic Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 3.16
Funders
- European Commission
- National Natural Science Foundation of China
- Austrian Science Fund
- Magyar Tudományos Akadémia
- Nemzeti Kutatási Fejlesztési és Innovációs Hivatal
- Nemzeti Kutatási, Fejlesztési és Innovaciós Alap
- National Research, Development and Innovation Office