A dynamic isotope effect in the nucleophilic substitution reaction between F− and CD3I

Year: 2025

Type: article

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. Crossed-beam reactive scattering experiments of a nucleophilic substitution reaction show a dynamic isotope effect with a remarkable deviation from quasiclassical calculations, which is evidence for quantum dynamics in this ion-molecule reaction.

Source: Nature Communications

DOI: 10.1038/s41467-025-57086-0

Authors: Atilay Ayasli, Arnab Khan, Thomas Gstir, Tim Michaelsen, Dóra Papp, Yan Wang, Hongwei Song, Minghui Yang, Gábor Czakó, Roland Wester

Institutions: Universität Innsbruck, Indian Institute of Science Education and Research, Bhopal, University of Szeged, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, CAS, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,990

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

OpenAlex ID: W4408246815