Pilankatta K Ramya, Ayush Shivhare, Milind M. Deshmukh, Cherumuttathu Hariharan Suresh
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The interconversion between <em>lbi</em> and <em>sbi</em> occurs through a transition state. The study highlights the crucial role of electron transfer in BSI, with <em>sbi</em> involving valence electron transfer from the metal to the hydrocarbon, leading to zwitterionic radical complexes. In contrast, <em>lbi</em> exhibit a slight electron density transfer from the hydrocarbon to the metal. The presence of low-energy transition states between <em>lbi</em> and <em>sbi</em> suggests a dynamic hopping mechanism for alkali metals, particularly Li, on hydrocarbon surfaces. The study identifies Li complexes as potential candidates for anode materials in batteries due to their stability and electron transfer properties, offering valuable insights into the design of advanced materials for energy storage applications.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"From Loose to Tight: Unveiling Bond Stretch Isomerism in π-Complexes of Li, Na and K\",\"authors\":\"Pilankatta K Ramya, Ayush Shivhare, Milind M. 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The study highlights the crucial role of electron transfer in BSI, with <em>sbi</em> involving valence electron transfer from the metal to the hydrocarbon, leading to zwitterionic radical complexes. In contrast, <em>lbi</em> exhibit a slight electron density transfer from the hydrocarbon to the metal. The presence of low-energy transition states between <em>lbi</em> and <em>sbi</em> suggests a dynamic hopping mechanism for alkali metals, particularly Li, on hydrocarbon surfaces. 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From Loose to Tight: Unveiling Bond Stretch Isomerism in π-Complexes of Li, Na and K
The study investigates the phenomenon of bond stretch isomerism (BSI) in complexes formed between alkali metals (Li, Na, K) and various non-aromatic, aromatic hydrocarbons, as well as heteroaromatic systems. The research employs density functional theory (DFT) calculations to optimize complex geometries and analyze their electronic structures using molecular electrostatic potential (MESP), charge, and spin density analyses. The results reveal that these complexes can exist in two distinct configurations: 'loose' long-bond isomers (lbi) that retain the original hydrocarbon geometry and 'tight' short-bond isomers (sbi) that undergo geometrical distortion upon complexation, with sbi generally being more stable. The interconversion between lbi and sbi occurs through a transition state. The study highlights the crucial role of electron transfer in BSI, with sbi involving valence electron transfer from the metal to the hydrocarbon, leading to zwitterionic radical complexes. In contrast, lbi exhibit a slight electron density transfer from the hydrocarbon to the metal. The presence of low-energy transition states between lbi and sbi suggests a dynamic hopping mechanism for alkali metals, particularly Li, on hydrocarbon surfaces. The study identifies Li complexes as potential candidates for anode materials in batteries due to their stability and electron transfer properties, offering valuable insights into the design of advanced materials for energy storage applications.
期刊介绍:
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.