Sigma radicals in gamma-irradiated single crystals of 2-thiothymine
文献信息
Thioanalogs of the nucleic-acid bases are known photosensitive probes and good traps of radiation energy. Radiation-induced sulfur-centered free radicals stabilized on the base thioanalogs molecules are of the cationic origin. Their electronic configuration is of the π type, unless an electron-donating group, like Cl−, is added to the sulfur atom, forming the σσ* “ three-electron” S∴Cl bond. The σ radical observed in irradiated 2-thiothymine is formed simply by deprotonation of the pristine cation radical. The 2σ character of the radical is determined from the nature of the g tensor and the A(14N) coupling tensor and their relation to the radical skeleton. The deprotonation of the cation radical takes place at N(3) rather than at N(1), generally observed in the irradiated pyrimidine natural bases and their other thioanalogs.
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Physical Chemistry Chemical Physics

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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