An ion soft-landing approach was applied to study the motion of hydronium (D(3)O(+)) and cesium (Cs(+)) ions from 84 to 104 K in glassy 3-methyl-pentane (3MP) films vapor deposited on Pt(111). Both ions were found to have very similar mobilities in 3MP. The span of ion mobilities probed is from approximately 10(-18) to approximately 10(-13) m(2) V(-1) s(-1). Ion transport in these films was studied as a function of film thickness and electric field strength. The drift velocity was found to be linear with applied field below about 2 x 10(8) Vm and deviated from linearity above this. To a large extent, D(3)O(+) and Cs(+) motion in 3MP was well predicted by a simple continuum-based ion mobility model in films from 25 to 20,000 ML thick (including pronounced perturbations 7 ML from both the vacuum and Pt interfaces). The mobility varied with temperature more slowly than predicted by Stokes' law, which may be due to extended inhomogeneous structures in the 3MP near its glass transition at 77 K.
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http://dx.doi.org/10.1063/1.2748756 | DOI Listing |
Angew Chem Int Ed Engl
October 2024
Higher Educational Key Laboratory for Nano Biomedical Technology of Fujian Province, Department of Pharmaceutical Analysis, Fujian Medical University, Fuzhou, 350004, China.
Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited-state proton-coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (HO) binding can trigger a nonlinear, pH-dependent excited-state concerted electron proton transfer (CEPT) reaction.
View Article and Find Full Text PDFSci Rep
October 2024
Institute for Quantum Life Science, National Institutes for Quantum Science and Technology, 4-9-1 Anagawa, Inage-ku, Chiba-shi, 263-8555, Japan.
Scientific insights into water photolysis and radiolysis are essential for estimating the direct and indirect effects of deoxyribonucleic acid (DNA) damage. Secondary electrons from radiolysis intricately associated with both effects. In our previous paper, we simulated the femtosecond (1 × 10 s) dynamics of secondary electrons ejected by energy depositions of 11-19 eV into water via high-energy electron transport using a time-dependent simulation code.
View Article and Find Full Text PDFJ Phys Chem B
October 2024
Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, United States.
Molecular dynamics simulations are used to examine the thermodynamic and structural aspects of the transfer of the classical hydronium ion (HO) across a water/1,2-dichloroethane (DCE) interface assisted by the phase-transfer catalyst (PTC) tetrakis(pentafluorophenyl) borate anion (TPFB). The free energy of transfer from water to DCE of the HO-TPFB ion pair is calculated to be 6 ± 1 kcal/mol, significantly less than that of the free hydronium ion (17 ± 1 kcal/mol). The ion pair is relatively stable at the interface and in the organic phase when it is accompanied by three water molecules with a small barrier to dissociation that supports its utility as a PTC.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Key Laboratory of Automobile Materials MOE, School of Materials Science & Engineering, Electron Microscopy Center, International Center of Future Science, Jilin Provincial International Cooperation Key Laboratory of High-Efficiency Clean Energy Materials, Jilin University, 130012, Changchun, China.
Collapsing and degradation of active materials caused by the electrode/electrolyte interface instability in aqueous batteries are one of the main obstacles that mitigate the capacity. Herein by reversing the notorious side reactions include the loss and dissolution of electrode materials, as we applied Ostwald ripening (OR) in the electrochemical cycling of a copper hexacyanoferrate electrode in a hydronium-ion batteries, the dissolved Cu and Fe ions undergo a crystallization process that creates a stable interface layer of cross-linked cubes on the electrode surface. The layer exposed the low-index crystal planes (100) and (110) through OR-induced electrode particle growth, supplemented by vacancy-ordered (100) superlattices that facilitated ion migration.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Institute for Integrated Catalysis and Physical Science Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
In the presence of water, hydronium ions formed within the micropores of zeolite H-BEA significantly influence the surrounding environment and the reactivity of organic substrates. The positive charge of these ions, coupled with the zeolite's negatively charged framework, results in an ionic environment that causes a strongly nonideal solvation behavior of cyclohexanol. This leads to a significantly higher excess chemical potential in the initial state and stabilizes at the same time the charged transition state in the dehydration of cyclohexanol.
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