Trujilloeliasen1577

Time-structured independent component analysis of the simulated trajectories quantitatively shows that cavity-solvent density contributes considerably in an optimized reaction coordinate involving cavity-ligand separation and water occupancy. Our approach quantifies two solvent-mediated macrostates at an intermediate separation of the cavity-ligand recognition pathways, apart from the fully ligand-bound and fully ligand-unbound macrostates. Interestingly, we find that these water-mediated intermediates, while transient in populations, can undergo slow mutual interconversion and create possibilities of multiple pathways of cavity recognition by the ligand. Overall, the work provides a quantitative assessment of the role that the solvent plays in facilitating the recognition process involving the hydrophobic cavity.The catalytic properties of metal oxides are often enabled by surface defects, and their characterization is thus vital to the understanding and application of metal oxide catalysts. Typically, surface defects for metal oxides show fingerprints in spectroscopic characterization. However, we found that synchrotron-radiation photoelectron spectroscopy (SRPES) is difficult to probe surface defects of ZnO. Meanwhile, CO as a probe molecule cannot be used properly to identify surface defect sites on ZnO in infrared (IR) spectroscopy. Instead, we found that formaldehyde could serve as a probe molecule, which is sensitive to surface defect sites and could titrate surface oxygen vacancies on ZnO, as evidenced in both SRPES and IR characterization. Density functional theory calculations revealed that formaldehyde dissociates to form formate species on the stoichiometric ZnO(101¯0) surface, while it dissociates to formyl species on Vo sites of the reduced ZnO(101¯0) surface instead. Furthermore, the mechanism of formaldehyde dehydrogenation on ZnO surfaces was also elucidated, while the generated hydrogen atoms are found to be stored in ZnO bulk from 423 K to 773 K, making ZnO an interesting (de)hydrogenation catalyst.Ionic liquids are widely used as electrolytes in electronic devices in which they are subject to nanoconfinement within nanopores or nanofilms. Because the intrinsic width of an electrical double layer is on the order of several nanometers, nanoconfinement is expected to fundamentally alter the double layer properties. Furthermore, in confined systems, a large portion of the ions are interfacial, e.g., at the electrode interface, leading to significant deviations of electrostatic screening and ion dynamics as compared to bulk properties. In this work, we systematically investigate the interference between electrical double layers for nanoconfined ionic liquids and the resulting influence on the structure, dynamics, and screening behavior. We perform molecular dynamics simulations for the ionic liquids [BMIm+][BF4 -] and [BMIm+][PF6 -] confined between two flat electrodes at systematic separation distances between 1.5 nm and 4.5 nm for both conducting and insulating boundary conditions. selleck compound We find that while ion dynamics is expectedly slower than in the bulk (by ∼2 orders of magnitude), there is an unexpected non-linear trend with the confinement length that leads to a local maximum in dynamic rates at ∼3.5-4.5 nm confinement. We show that this nonlinear trend is due to the ion correlation that arises from the interference between opposite double layers. We further evaluate confinement effects on the ion structure and capacitance and investigate the influence of electronic polarization of the ionic liquid on the resulting properties. This systematic evaluation of the connection between electrostatic screening and structure and dynamics of ionic liquids in confined systems is important for the fundamental understanding of electrochemical supercapacitors.Transport phenomena in organic, self-assembled molecular J-aggregates have long attracted a great deal of attention due to their potential role in designing novel organic photovoltaic devices. A large number of theoretical and experimental studies have been carried out describing excitonic energy transfer in J-aggregates under the assumption that excitons are induced by a coherent laser-light source or initialized by a localized excitation on a particular chromophore. However, these assumptions may not provide an accurate description to assess the efficiency of J-aggregates, particularly as building blocks of organic solar cells. Under natural conditions, J-aggregates would be subjected to an incoherent source of light (as is sunlight), which would illuminate the whole photosynthetic complex rather than a single molecule. In this work, we present the first study of the efficiency of photosynthetic energy transport in self-assembled molecular aggregates under incoherent sunlight illumination. By making use of a minimalistic model of a cyanine dye J-aggregate, we demonstrate that long-range transport efficiency is enhanced when exciting the aggregate with incoherent light. Our results thus support the conclusion that J-aggregates are, indeed, excellent candidates for devices where efficient long-range incoherently induced exciton transport is desired, such as in highly efficient organic solar cells.Steady-state and time-resolved fluorescence techniques were employed to study the excited-state proton transfer (ESPT) from a reversibly dissociating photoacid, 2-naphthol-6,8-disulfonate (2N68DS). The reaction was carried out in water and in acetonitrile-water solutions. We find by carefully analyzing the geminate recombination dynamics of the photobase-proton pair that follows the ESPT reaction that there are two targets for the proton back-recombination reaction the original O- dissociation site and the SO3 - side group at the 8 position which is closest to the proton OH dissociation site. This observation is corroborated in acetonitrile-water mixtures of χwater 0.23 the band resembles the free anion band observed in pure water. Concomitantly, the ESPT rate increases when χwater increases because the intermolecular ESPT to the solvent (bulk water) gradually prevails over the much slower intramolecular via the water-bridges ESPT process.