Hydride shift in substituted phenyl glyoxals: Interpretation of experimental rate data using electronic structure and variational transition state theory calculations

Literature Information

Publication Date 2001-08-28
DOI 10.1039/B102330F
Impact Factor 3.676
Authors

Gary Tresadern, Julie Willis, Ian H. Hillier, C. Ian F. Watt


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Abstract

Experimental rate data for hydride transfer in some p-substituted phenyl glyoxals in 80: 20 dioxan:water are presented including kinetic hydrogen isotope effects. The roles of different substituents are discussed using electronic structure calculations of the potential energy surfaces at the SM5.4/PM3 level together with calculations employing variational transition state theory and multidimensional tunneling. p-NO2 substitution has the most pronounced effect on the rate parameters, which can be understood in terms of the relative destabilisation of the reactant and reduced quantum mechanical tunneling through the barrier. The use of different models for tunneling suggests that when coupled with the SM5.4/PM3 method, the higher level of theories tend to overestimate the degree of tunneling.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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