High-level analytical potential-energy-surface-based dynamics of the OH− + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions

András B. Nacsa; Csenge Tokaji; Gábor Czakó

doi:10.1039/D3FD00161J

You do not have JavaScript enabled. Please enable JavaScript to access the full features of the site or access our non-JavaScript page.

High-level analytical potential-energy-surface-based dynamics of the OH⁻ + CH₃CH₂Cl S_N2 and E2 reactions in full (24) dimensions†

András B. Nacsa,

^a Csenge Tokaji^a and Gábor Czakó

*^a

Author affiliations

* Corresponding authors

^a MTA-SZTE Lendület Computational Reaction Dynamics Research Group, Interdisciplinary Excellence Centre and Department of Physical Chemistry and Materials Science, Institute of Chemistry, University of Szeged, Rerrich Béla tér 1, Szeged H-6720, Hungary
E-mail: gczako@chem.u-szeged.hu

Abstract

We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH⁻ + CH₃CH₂Cl reactive system, using the Robosurfer program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with Molpro and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular nucleophilic substitution (S_N2) and elimination (E2) channels leading to the Cl⁻ + CH₃CH₂OH and Cl⁻ + H₂O + C₂H₄ products, respectively, and allows efficient quasi-classical trajectory (QCT) simulations. QCT computations on the new PES provide accurate statistically-converged integral and differential cross sections for the OH⁻ + CH₃CH₂Cl reaction, revealing the competing dynamics and mechanisms of the S_N2 and E2 (anti, syn, β–α transfer) channels as well as various additional pathways leading to induced inversion of the CH₃CH₂Cl reactant, H-exchange between the reactants, H₂O⋯Cl⁻ complex formation, and H₂O + CH₃CHCl⁻ products via proton abstraction.

This article is part of the themed collection: New directions in molecular scattering

Download options Please wait...

Associated articles

Scattering of larger molecules – part 2: general discussion

Supplementary files

Supplementary information PDF (699K)

Article information

DOI: https://doi.org/10.1039/D3FD00161J
Article type: Paper
Submitted: 08 Dec 2023
Accepted: 20 Feb 2024
First published: 21 Feb 2024
This article is Open Access

Download Citation

Faraday Discuss., 2024,251, 604-621

Permissions

Request permissions

High-level analytical potential-energy-surface-based dynamics of the OH⁻ + CH₃CH₂Cl S_N2 and E2 reactions in full (24) dimensions

A. B. Nacsa, C. Tokaji and G. Czakó, Faraday Discuss., 2024, 251, 604 DOI: 10.1039/D3FD00161J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Social activity

Fetching data from CrossRef.
This may take some time to load.

Faraday Discussions