Isotope effect on the J–T distortion of partially deuteriated benzenecation radicals: an experimental EPR and theoretical DFT study

Literature Information

Publication Date 2004-02-27
DOI 10.1039/B315835G
Impact Factor 3.676
Authors

Kazumi Toriyama, Masaharu Okazaki, Magnus Jansson, Anders Lund, Sten Lunell


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Abstract

D/H isotope-substitution effects on the Jahn–Teller (J–T) distortion of cation radicals of partially deuteriated benzenes; benzene-d5, benzene-1,2,4,5-d4, benzene-1,4-d2, and benzene-1,3,5-d3, were investigated by electron spin resonance (EPR) using frozen haloalkanes and porous silicas as matrices. Quantum-chemical calculations using the density functional theory (DFT) method were also performed. The way of distortion of the cation radicals of selectively deuteriated benzenes is unique relative to the deuteriation sites in all the matrices used. The ground state of the distorted cation is 2B2g of D2h symmetry, regardless of the way of isotope labeling. The undeuteriated C–H bonds occupy the specific positions in the distorted form where the higher spin density appears, in agreement with the result of theoretical calculations. The role of the matrix to stabilize the distorted form is also discussed.

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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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