DFT study of inner-sphere electron transfer in a gas-phase SN2 reaction at the saturated carbon

Literature Information

Publication Date 2002-09-02
DOI 10.1039/B202613A
Impact Factor 3.676
Authors

Yu-Mei Xing, Xiu-Fang Xu, Lan Chen, Zun-Sheng Cai, Xue-Zhuang Zhao, Jin-Pei Cheng


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Abstract

The SN2 reaction is investigated from the point of view of an inner-sphere electron transfer reaction. Density functional theory (DFT) calculations are applied to investigate the intrinsic reaction pathway (IRP) of the symmetrical SN2 (inner-sphere electron transfer) reactions, Xa− + CH3Xb → XaCH3 + Xb− (X = F, Cl, Br, I). The geometries of the stationary points in the potential energy surface are compared with available experimental data and with calculations at the MP2 level. The changes in the geometrical parameters, the projected frequencies, charge distribution and dipole moment along the reaction coordinate are discussed. Some relationships between the amount of transferred electron density and the changes in geometrical parameters, vibrational frequencies and energies are given: the greater the amount of transferred electron density, the smaller the decrease in the frequency of the C–Xb stretching mode (from reactant to TS), and the lower the activation energy and the complexation energy. Moreover, the amount of transferred electron density is related to the electronegativity of the halogen atom. Two parameters in the electron transfer theory, the coupling interaction and the reorganization energy, which affect the reactivity are discussed. We conclude that the stronger the CH3–Xb bond, the worse the acceptor.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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