Fano resonances in the photoinduced H-atom elimination dynamics in the πσ* states of pyrrole
文献信息
Sergy Yu. Grebenshchikov, David Picconi
Fano resonances are predicted to be prominent features of the πσ* photochemistry of pyrrole. The Fano interference leads to distorted absorption bands and internally hot photofragments. The interference, studied using high level ab initio theory and quantum mechanics, is supported by two distinct dynamical scenarios controlled by two exit channel conical intersections between the πσ* states and the ground electronic state . For the lowest state 1A2(πσ*), the coupling at the conical intersection is weak, and the interfering dissociation pathways are diabatic; for the higher lying 1B1(πσ*) state, the coupling at the conical intersection is strong, and the interfering dissociation pathways are adiabatic. Both scenarios persist with increasing number of degrees of freedom included in the dynamic modelling. They are expected to be operative in the πσ* photochemistry of a broad class of model UV biochromophores.
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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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