Computational investigation of the photoinduced homolytic dissociation of water in the pyridine–water complex
文献情報
Andrzej L. Sobolewski, Raffaele Borrelli, Wolfgang Domcke
The photochemistry of the hydrogen-bonded pyridine–water complex has been investigated with ab initio computational methods. Vertical excitation energies, excited-state reaction paths for proton transfer as well as structures and energies of conical intersections and reaction barriers have been determined with multi-configuration self-consistent-field and multi-reference perturbation methods, as well as with single-reference coupled-cluster and propagator methods. In the pyridine–water complex, the energies of two charge-separated excited states of 1nπ* and 1ππ* character are connected to the energies of the locally excited 1nπ* and 1ππ* states of the pyridine chromophore via a low energy barrier. The charge-separated excited states are strongly stabilized by the transfer of a proton from water to pyridine. The energies of the resulting biradical states intersect the potential-energy surface of the closed-shell ground state as a function of the proton-transfer coordinate. The resulting radical pair may dissociate to yield pyridinium and hydroxyl radicals. The photochemistry of the hypervalent pyridinium radical has been explored with the same computational methods. It has been found that a low-lying dissociative 2πσ* excited state exists in pyridinium, which can lead to the photodetachment of the hydrogen atom. Overall, the H2O molecule can thus be dissociated into H˙ and OH˙ radicals by the absorption of two ultraviolet photons. The relevance of these results for solar water splitting and solar carbon dioxide reduction is discussed.
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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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