A benchmark ab initio study of the complex potential energy surfaces of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions

Tasi, Domonkos A.; Tokaji, Csenge; Czakó, Gábor

doi:10.1039/d1cp01303c

Cited by 11 publications

(25 citation statements)

References 54 publications

(73 reference statements)

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“…The mean absolute error (MAE) of MP2 and CCSD(T)/PP/t methods relative to experimental values are 5.1 and 4.0 kcal mol À1 , respectively. We noticed that Domokos et al 41 obtained similar values using MP2/aug-cc-pVDZ, similar to our MP2/ECP/d method, and their CCSD(T)-F12b/aug-cc-pVQZ (+ DZPE[CCSD(T)-F12b/aug-cc-pVDZ]) method gave values which are in excellent agreement with the experimental values.…”

Section: Resultssupporting

confidence: 88%

“…We note that during the preparation of this manuscript, the Czako ´group carried out a benchmark study on the non-solvated HO À + CH 3 CH 2 X reaction using a high-level explicitly-correlated CCSD(T)-F12b method. 41 Therefore, a thorough characterization of the reaction PESs for the titled reaction HO À + CH 3 CH 2 X using the microsolvation model is of considerable interest.…”

Section: Introductionmentioning

confidence: 99%

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Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Zhang

Xie

2022

Phys. Chem. Chem. Phys.

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Section: Resultssupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Zhang

Xie

2022

Phys. Chem. Chem. Phys.

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“… b The relative energies of OH – + CH 3 CH 2 Cl reaction at CCSD(T)-F12b/aug-cc-pVQZ level is from ref . …”

Section: Resultsmentioning

confidence: 99%

“…Besides, the ionic radii of the nucleophile show the following increasing order of F − (1. 26 28 that is, the nucleophile becomes bulkier following the order F − < Cl − < Br − < I − . Variation of the nucleophiles from F − to I − leads to the elongation of X−C α in RC2, which indicated that the ion−dipole complex becomes more weakly bonded.…”

Section: Entrance Channel Complexesmentioning

confidence: 99%

Nucleophile Effects on the E2/S_N2 Competition for the X^– + CH₃CH₂Cl Reactions: A Theoretical Study

Zhao

Zhen

et al. 2023

J. Phys. Chem. A

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The effect of nucleophiles on the gas-phase E2/SN2 competition is still not completely elucidated, despite its importance in chemistry. In the current work, the electronic structure calculations of prototypical reactions X– + CH3CH2Cl (X = OH, F, Cl, Br, and I) are performed at the MP2 level with aug-cc-pVDZ or ECP/d. The effects of nucleophiles on the competing E2 and SN2 reactions in terms of the correlation between the barrier height and reaction energy, electronegativity of X, bond length, charge distribution, and proton affinity of anionic nucleophile X– are explored and emphasized. As the nucleophile changes from OH– to I–, both SN2 and E2 reactions become more exothermic, with the reaction energy in the ranges from −51.9 to 10.8 kcal mol–1 (SN2) and −36.8 to 38.0 kcal mol–1(E2). For X– = F– and OH–, the sequence of reactivity for the four pathways is ret-SN2 < syn-E2 < anti-E2 ∼ inv-SN2. However, for X– = Cl–, Br–, and I–, the anti-E2 barrier is much higher in energy (17.1–29.4 kcal mol–1) than that of inv-SN2. Energy decomposition analysis illustrates that the anti-E2 pathway possesses the highly destabilizing characteristic distortion, resulting in a larger reaction barrier and hence becoming a more unfavorable pathway than inv-SN2. More interestingly, only ion–dipole complex exists in the entrance channel for reactions involving OH–, Cl–, Br–, and I–, and in contrast, a significant hydrogen-bonded complex formation is also revealed for X– = F–, which can further affect E2/SN2 competition and atomic-level mechanisms, especially, for the isoelectronic nucleophile F– and OH–. It has been revealed here that electronegativity of central atoms in X and ionic radii of nucleophiles are the important factors affecting the entrance channel complex.

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“…From a theoretical point of view, the potential energy, 21 reaction dynamics, 22–24 steric 25 and solvent effects, 26–28 and quantum scattering 29 have been studied using ab initio calculations by several research groups. For example, the effects of micro-solvation on the OH − + CH 3 I reaction were investigated using the direct dynamics simulation, 30 which demonstrated that while the S N 2 reaction dominated at all reactant collision energies, proton transfer to form CH 2 I − was found to dominate at higher collision energies.…”

Section: Introductionmentioning

confidence: 99%

Reaction mechanism of an intracluster S_N2 reaction induced by electron capture

Tachikawa¹

2022

Phys. Chem. Chem. Phys.

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A benchmark ab initio study of the complex potential energy surfaces of the OH⁻ + CH₃CH₂Y [Y = F, Cl, Br, I] reactions

Abstract: We provide the first benchmark characterization of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions utilizing the high-level explicitly-correlated CCSD(T)-F12b method with the aug-cc-pVnZ [n = 2(D),...

Cited by 11 publications

References 54 publications

Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Nucleophile Effects on the E2/S_N2 Competition for the X^– + CH₃CH₂Cl Reactions: A Theoretical Study

Reaction mechanism of an intracluster S_N2 reaction induced by electron capture

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A benchmark ab initio study of the complex potential energy surfaces of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions

Abstract: We provide the first benchmark characterization of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions utilizing the high-level explicitly-correlated CCSD(T)-F12b method with the aug-cc-pVnZ [n = 2(D),...

Cited by 11 publications

References 54 publications

Investigating the competing E2 and SN2 mechanisms for the microsolvated HO−(H2O)n=0–4 + CH3CH2X (X = Cl, Br, I) reactions

Investigating the competing E2 and SN2 mechanisms for the microsolvated HO−(H2O)n=0–4 + CH3CH2X (X = Cl, Br, I) reactions

Nucleophile Effects on the E2/SN2 Competition for the X– + CH3CH2Cl Reactions: A Theoretical Study

Reaction mechanism of an intracluster SN2 reaction induced by electron capture

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A benchmark ab initio study of the complex potential energy surfaces of the OH⁻ + CH₃CH₂Y [Y = F, Cl, Br, I] reactions

Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Investigating the competing E2 and S_N2 mechanisms for the microsolvated HO⁻(H₂O)_n=0–4 + CH₃CH₂X (X = Cl, Br, I) reactions

Nucleophile Effects on the E2/S_N2 Competition for the X^– + CH₃CH₂Cl Reactions: A Theoretical Study

Reaction mechanism of an intracluster S_N2 reaction induced by electron capture