The driving forces for twisted or planar intramolecular charge transfer
文献信息
A D–A (donor–acceptor)-type chromophore may twist or flatten in its excited state to form a TICT (twisted intramolecular charge transfer) state or a PICT (planar intramolecular charge transfer) state, respectively. What is the driving force behind this twisting or planarization? Which geometry will occur for a certain D–A chromophore? To answer these questions, both fragment orbital interaction and excited state energy decomposition analyses were performed on several classical TICT/PICT molecules. Three driving forces were identified, namely, energy gap, hole–electron interactions, and excited state relaxation. The contributions of these driving forces in various types of molecules were analyzed to determine how the molecular structure affects them. The energy gap difference between the twisted and planar geometries was found to play a decisive role in most situations. Thus, evaluating the frontier orbital interactions between the donor and acceptor effectively predicts whether chromophores planarize or twist in the excited state.
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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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