We report experimental verification of the Smoluchowski theory for diffusion-controlled reactions in solution at the steady-state limit. We have determined both the diffusion coefficients and the self-termination reaction rates of the diphenylmethyl radical simultaneously. Smoluchowski theory is insufficient to discuss the reaction rate for the self-termination reaction of the diphenylmethyl radical, so the reaction rate of an encounter complex based on the Collins-Kimball treatment is estimated.
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Spectrochim Acta A Mol Biomol Spectrosc
January 2025
Institute of Chemistry, Military University of Technology, Kaliskiego 2, PL-00908 Warsaw, Poland.
Molecular arrangement in the chiral smectic phases of the glassforming (S)-4'-(1-methylheptylcarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]benzoate is investigated by X-ray diffraction. An increased correlation length of the positional short-range order in the supercooled state agrees with the previous assumption of the hexatic smectic phase. However, the registered X-ray diffraction patterns are not typical for the hexatic phases.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Section on Molecular Transport, Eunice Kennedy Shriver National Institute of Child Health and Human Development, National Institutes of Health, Bethesda, Maryland 20892, USA.
One of the most subtle steps in the single-molecule approach to the flux through the membrane channel, which uses the one-dimensional Smoluchowski equation, is to describe the molecule's "behavior" at the contacts between the channel openings and the bulk. Earlier, to handle this issue, we introduced the so-called "radiation boundary conditions" that account for the interplay between the two types of trajectories of the molecules starting at the openings, specifically, the ones that eventually return to the channel and the ones that escape to infinity. The latter trajectories represent the true translocation events on the condition that initially the molecule entered the channel from the opposite side.
View Article and Find Full Text PDFJ Neural Eng
January 2025
Center for Complex Systems and Brain Sciences, Universidad Nacional de San Martin Escuela de Ciencia Y Tecnologia, 25 de Mayo y Francia, San Martín, Buenos Aires, 1650, ARGENTINA.
Objective Magnetic resonance imaging (MRI), functional MRI (fMRI) and other neuroimaging techniques are routinely used in medical diagnosis, cognitive neuroscience or recently in brain decoding. They produce three- or four-dimensional scans reflecting the geometry of brain tissue or activity, which is highly correlated temporally and spatially. While there exist numerous theoretically guided methods for analyzing correlations in one-dimensional data, they often cannot be readily generalized to the multidimensional geometrically embedded setting.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2024
Department of Surface and Plasma Science, Charles University, Prague 18000, Czech Republic.
Perovskites exhibit outstanding performance in applications such as photocatalysis, electrochemistry, or photovoltaics, yet their practical use is hindered by the instability of these materials under operating conditions, specifically caused by the segregation of alkali cations toward the surface. The problem arises from the bulk strain related to different cation sizes, as well as the inherent electrostatic instability of perovskite surfaces. Here, we focus on atomistic details of the surface-driven process of interlayer switching of alkali atoms at the inorganic perovskite surface.
View Article and Find Full Text PDFPhys Rev Lett
November 2024
Skolkovo Institute of Science and Technology, 121205 Moscow, Russia.
We derive from the first principles new hydrodynamic equations-Smoluchowski-Euler equations for aggregation kinetics in space-inhomogeneous fluids with fluxes. Starting from Boltzmann equations, we obtain microscopic expressions for aggregation rates for clusters of different sizes and observe that they significantly differ from currently used phenomenological rates. Moreover, we show that for a complete description of aggregating systems, novel kinetic coefficients are needed.
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