Unknown

Dataset Information

0

A dynamic isotope effect in the nucleophilic substitution reaction between F<sup>-</sup> and CD<sub>3</sub>I.

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.

SUBMITTER: Ayasli A 

PROVIDER: S-EPMC11890872 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

A dynamic isotope effect in the nucleophilic substitution reaction between F&lt;sup&gt;-&lt;/sup&gt; and CD&lt;sub&gt;3&lt;/sub&gt;I.

Ayasli Atilay A   Khan Arnab A   Gstir Thomas T   Michaelsen Tim T   Papp Dóra D   Wang Yan Y   Song Hongwei H   Song Hongwei H   Yang Minghui M   Czakó Gábor G   Wester Roland R  

Nature communications 20250308 1

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 ato  ...[more]

Similar Datasets

Unknown Atomistic dynamics of elimination and nucleophilic substitution disentangled for the F&lt;sup&gt;-&lt;/sup&gt; + CH&lt;sub&gt;3&lt;/sub&gt;CH&lt;sub&gt;2&lt;/sub&gt;Cl reaction.
| S-EPMC7611763 | biostudies-literature
Unknown Oxidation-induced nucleophilic substitution at the electron-rich B(12) vertex in [CB&lt;sub&gt;11&lt;/sub&gt;H&lt;sub&gt;12&lt;/sub&gt;]&lt;sup&gt;-&lt;/sup&gt; under catalyst-free conditions.
| S-EPMC11884434 | biostudies-literature
Unknown Dynamic origin of the stereoselectivity of a nucleophilic substitution reaction.
| S-EPMC3417076 | biostudies-literature
Unknown Fenton-Inactive Cd Enables Highly Selective O&lt;sub&gt;2&lt;/sub&gt;-Derived Domino Reaction.
| S-EPMC11653596 | biostudies-literature
Unknown Reaction Dynamics of the H + HeH&lt;sup&gt;+&lt;/sup&gt; → He + H&lt;sub&gt;2&lt;/sub&gt; &lt;sup&gt;+&lt;/sup&gt; System.
| S-EPMC12648427 | biostudies-literature
Unknown Cs&lt;sub&gt;2&lt;/sub&gt;CO&lt;sub&gt;3&lt;/sub&gt;-N,N-Dimethylacetamide-Promoted Esterification of Arylformic Acids with a-Bromo Esters via Nucleophilic Substitution.
| S-EPMC12518028 | biostudies-literature
Unknown Homometallic 2D Cd&lt;sup&gt;2+&lt;/sup&gt; and Heterometallic 3D Cd&lt;sup&gt;2+&lt;/sup&gt;/Ca&lt;sup&gt;2+&lt;/sup&gt;, Cd&lt;sup&gt;2+&lt;/sup&gt;/Sr&lt;sup&gt;2+&lt;/sup&gt; Metal-Organic Frameworks Based on an Angular Tetracarboxylic Ligand.
| S-EPMC12565934 | biostudies-literature
Unknown UDP-glucose Dehydrogenase: The First-step Oxidation Is an NAD<sup>+</sup>-dependent Bimolecular Nucleophilic Substitution Reaction (S<sub>N</sub>2).
| S-EPMC6367545 | biostudies-literature
Unknown Immobilization of a [Co&lt;sup&gt;III&lt;/sup&gt;Co&lt;sup&gt;II&lt;/sup&gt;(H&lt;sub&gt;2&lt;/sub&gt;O)W&lt;sub&gt;11&lt;/sub&gt;O&lt;sub&gt;39&lt;/sub&gt;]&lt;sup&gt;7-&lt;/sup&gt; Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction.
| S-EPMC9284608 | biostudies-literature
Unknown Effects of Isomorphous Substitution on Photophysical and Magnetic Properties of Complexes [Ln&lt;sub&gt;1-&lt;/sub&gt; &lt;sub&gt;x&lt;/sub&gt;Dy&lt;sub&gt;x&lt;/sub&gt;(MeDPQ)&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;3&lt;/sub&gt;] (Ln = Y&lt;sup&gt;3+&lt;/sup&gt;, Ho&lt;sup&gt;3+&lt;/sup&gt;, and Er&lt;sup&gt;3+&lt;/sup&gt;).
| S-EPMC12648457 | biostudies-literature