Unimolecular decay of the Cl−···CH3Cl complex: Influence of symmetry breaking

文献信息

发布日期 2001-04-27
DOI 10.1039/B009879P
影响因子 3.676
作者

S. Schmatz, P. Botschwina


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摘要

The unimolecular dissociation of quasi-bound states formed in the bimolecular nucleophilic substitution (SN2) reaction 35Cl− + CH337Cl is investigated by means of two-dimensional quantum mechanical calculations. The study, which extends our recent work on the symmetric [35ClCH335Cl]− complex, highlights the changes in the dissociation rates when the symmetry with respect to the interchange of the two chlorine atoms is reduced. It is observed that in the intermediate energy range the distribution of rates is similar to the distribution for the gerade states in the case of the symmetric mass combination; rates, which are as small as the smallest rates for the ungerade states, are missing when different chlorine isotopes are used. An explanation of this effect is given in terms of an adiabatic model with emphasis on the non-adiabatic matrix elements, which promote transitions between different adiabatic states.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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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