High-level ab initio potential energy surface and dynamics of the F(-) + CH3I SN2 and proton-transfer reactions

Chemical Science
Balázs OlaszGábor Czakó

Abstract

Bimolecular nucleophilic substitution (SN2) and proton transfer are fundamental processes in chemistry and F(-) + CH3I is an important prototype of these reactions. Here we develop the first full-dimensional ab initio analytical potential energy surface (PES) for the F(-) + CH3I system using a permutationally invariant fit of high-level composite energies obtained with the combination of the explicitly-correlated CCSD(T)-F12b method, the aug-cc-pVTZ basis, core electron correlation effects, and a relativistic effective core potential for iodine. The PES accurately describes the SN2 channel producing I(-) + CH3F via Walden-inversion, front-side attack, and double-inversion pathways as well as the proton-transfer channel leading to HF + CH2I(-). The relative energies of the stationary points on the PES agree well with the new explicitly-correlated all-electron CCSD(T)-F12b/QZ-quality benchmark values. Quasiclassical trajectory computations on the PES show that the proton transfer becomes significant at high collision energies and double-inversion as well as front-side attack trajectories can occur. The computed broad angular distributions and hot internal energy distributions indicate the dominance of indirect mechanisms at lower...Continue Reading

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Citations

Jun 10, 2017·The Journal of Physical Chemistry Letters·István SzabóGábor Czakó
Jul 21, 2017·Physical Chemistry Chemical Physics : PCCP·Yong-Tao MaWilliam L Hase
Aug 18, 2017·Physical Chemistry Chemical Physics : PCCP·Xu LiuRui Sun
Nov 15, 2017·Chemical Society Reviews·Eduardo CarrascosaRoland Wester
Jan 9, 2019·Physical Chemistry Chemical Physics : PCCP·Balázs Olasz, Gábor Czakó
Mar 29, 2019·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
Feb 6, 2020·Physical Chemistry Chemical Physics : PCCP·Domonkos A TasiGábor Czakó
May 27, 2020·Physical Chemistry Chemical Physics : PCCP·Yan LiDunyou Wang
Apr 22, 2020·Annual Review of Physical Chemistry·Bhumika Jayee, William L Hase
Nov 13, 2019·Journal of Computational Chemistry·Nandini SavooJordi Poater
Jul 10, 2018·Science Advances·Martin SteiRoland Wester
Feb 16, 2021·Physical Chemistry Chemical Physics : PCCP·Xiaoyan JiJing Xie
Jun 2, 2021·Mass Spectrometry Reviews·Roland Wester
Nov 18, 2018·The Journal of Physical Chemistry. a·Xu LiuJianmin Sun
Feb 13, 2020·The Journal of Physical Chemistry. a·Björn BastianRoland Wester
Jul 12, 2017·The Journal of Physical Chemistry. a·István Szabó, Gábor Czakó
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Oct 7, 2017·The Journal of Physical Chemistry. a·István Szabó, Gábor Czakó
Mar 25, 2017·The Journal of Physical Chemistry. a·Viktor Tajti, Gábor Czakó
Dec 19, 2019·Journal of Chemical Theory and Computation·Tibor Győri, Gábor Czakó
Mar 17, 2018·The Journal of Physical Chemistry. a·Tibor GyőriGábor Czakó
Sep 20, 2018·The Journal of Physical Chemistry. a·Balázs Olasz, Gábor Czakó
Sep 25, 2020·The Journal of Physical Chemistry Letters·Jun LiHua Guo
Oct 29, 2021·The Journal of Physical Chemistry. a·Attila Á DékányGábor Czakó

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