Toward exceeding the Shockley-Queisser limit: photoinduced interfacial charge transfer processes that store energy in excess of the equilibrated excited state

Nanocrystalline (anatase), mesoporous TiO2 thin films were functionalized with [Ru(bpy)2(deebq)](PF6)2, [Ru(bq)2(deeb)](PF6)2, [Ru(deebq)2(bpy)](PF6)2, [Ru(bpy)(deebq)(NCS)2], or [Os(bpy)2(deebq)](PF6)2, where bpy is 2,2'-bipyridine, bq is 2,2'-biquinoline, and deeb and deebq are 4,4'-diethylester derivatives. These compounds bind to the nanocrystalline TiO2 films in their carboxylate forms with limiting surface coverages of 8 (+/- 2) x 10(-8) mol/cm2. Electrochemical measurements show that the first reduction of these compounds (-0.70 V vs SCE) occurs prior to TiO2 reduction. Steady state illumination in the presence of the sacrificial electron donor triethylamine leads to the appearance of the reduced sensitizer. The thermally equilibrated metal-to-ligand charge-transfer excited state and the reduced form of these compounds do not inject electrons into TiO2. Nanosecond transient absorption measurements demonstrate the formation of an extremely long-lived charge separated state based on equal concentrations of the reduced and oxidized compounds. The results are consistent with a mechanism of ultrafast excited-state injection into TiO2 followed by interfacial electron transfer to a ground-state compound. The quantum yield for this process was found to increase with excitation energy, a behavior attributed to stronger overlap between the excited sensitizer and the semiconductor acceptor states. For example, the quantum yields for [Os(bpy)2(dcbq)]/TiO2 were phi(417 nm) = 0.18 +/- 0.02, phi(532.5 nm) = 0.08 +/- 0.02, and phi(683 nm) = 0.05 +/- 0.01. Electron transfer to yield ground-state products occurs by lateral intermolecular charge transfer. The driving force for charge recombination was in excess of that stored in the photoluminescent excited state. Chronoabsorption measurements indicate that ligand-based intermolecular electron transfer was an order of magnitude faster than metal-centered intermolecular hole transfer. Charge recombination was quantified with the Kohlrausch-Williams-Watts model.     

Stability of self-assembled monolayers on titanium and gold

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.     

High precision study of muon catalyzed fusion in D2 and HD gas

Muon catalyzed dd fusion in D₂ and HD gases in the temperature range from 28 to 350 K was investigated in a series of experiments based on a time-projection ionization chamber operating with pure hydrogen. All main observables in this reaction chain were measured with high absolute precision including the resonant and non-resonant ddμ formation rates, the rate for hyperfine transitions in dμ atoms, the branching ratio of the two charge symmetric fusion channels ³He + n and t + p and the muon sticking probability. The report presents the final analysis of the data together with a comprehensive comparison with calculations based on recent μCF theories. The energy of the loosely bound ddμ state with quantum numbers J = 1, ν = 1, which is central to the mechanism of resonant molecule formation, is extracted with precision ?₁₁(fit) = ?1.9651(7) eV. in impressive agreement with the latest theoretical results ?₁₁(theory) = ?1.9646 eV.     

Green light radiation effects on free radicals inhibition in cellular and chemical systems

Free radicals generation is inhibited through green light (GL) irradiation in cellular systems and in chemical reactions. Standard melanocyte cultures were UV-irradiated and the induced cellular reactive oxygen species (ROS) were quantified by the fluorescence technique. The same cell cultures, previously protected by a 24h GL exposure, displayed a significantly lower ROS production. A simple chemical reaction is subsequently chosen, in which the production of free radicals is well defined. Paraffin wax and mineral oil were GL irradiated during thermal degradation and the oxidation products checked by chemiluminescence [CL] and Fourier transform infrared spectra [FT-IR]. The same clear inhibition of the radical oxidation of alkanes is recorded. A quantum chemistry modeling of these results is performed and a mechanism involving a new type of Rydberg macromolecular systems with implications for biology and medicine is suggested.     

Untersuchungen von Formaldehydeiweiß

Ohne Zusammenfassung     

Behaviour of Bu(CH2—CHCH2)SnCl2 in water and water-cosolvent media: An approach to understanding the chemical degradation of organotins in aquatic environments

The behaviour of allylbutyltin dichloride in water, water–ethanol and water–hexane media, under either homogeneous or heterogeneous conditions, has been studied. 1,3-Diallyl-1,3-dibutyl-1,3-dichlorodistannoxane, butyltin di(hydroxy)chloride and butyltin trichloride arise from the solvolytic, acid–base and degradation processes. The degradation process involving the cleavage of the tin–carbon allyl bond has been interpreted to occur via an intramolecular reaction at the expense of the cation [Bu(CH₂=CHCH₂)Sn(OH)(H₂O)_n]⁺. The mechanistic pathway is ascribable to an internal interaction of the electrophilic cation with a bonded water molecule. This mechanistic proposal may be of some help with understanding of the chemical degradation of diorganotin derivatives in aquatic environments.     

The VIP Experimental Limit on the Pauli Exclusion Principle Violation by Electrons

In this paper we describe an experimental test of the validity of the Pauli Exclusion Principle (for electrons) which is based on a straightforward idea put forward a few years ago by Ramberg and Snow (Phys. Lett. B 238:438, 1990). We perform a very accurate search of X-rays from the Pauli-forbidden atomic transitions of electrons in the already filled 1S shells of copper atoms. Although the experiment has a very simple structure, it poses deep conceptual and interpretational problems. Here we describe the experimental method and recent experimental results, which we interpret in the framework of quon theory. We also present future plans to upgrade the experimental apparatus using Silicon Drift Detectors.     

The contribution of space charge in a high non-homogenous electric field to the creation of negative differential conductivity

The paper describes anomaly origination on current or voltage characteristics in time of positive potential on small curvature radius electrode rod against plane electrodes. An anomaly phenomenon occurred in the narrow voltage area in a high non-homogenous electric field close to the electrode (E > 10⁷ V m^?1). A mathematical – physical analysis of the observed processes in close proximity to the electrode with the above mentioned form is made. The differential equations, which analytically and theoretically describe this phenomenon, are compiled and solved. The space charge created by element particles (electrons, ions) which causes negative differential conductivity origination in narrow voltage area by their behaviour in electric field, plays a substantial role in this phenomenon. Current–voltage characteristics at both polarities of corona electrode were continuously measured at the study of static and dynamic processes occurring during discharge in the surrounding of a small curvature radius electrode. It was proved that an anomaly, in the form of negative differential conductivity (dI/dU < 0), appeared on a highly curved electrode at positive polarity in a narrow voltage area. This phenomenon was subjected to detailed experimental research including investigation of the influence of the shape and material of the electrode (output voltage), electrode temperature, influence of photoionization on the profile of the anomaly, the contribution of exoelectrons to particle distribution, and study of electrochemical potential of metal electrode. Oscillation of low ionized plasma at positive and negative polarity of small curvature radius electrodes has been analyzed. At the same time, the influence of the external forced electric field on the change of current–voltage characteristic profile was investigated. Theoretical justification of the anomaly phenomenon resulted from a change of energy conditions in the investigated place (the distance limit from the electrode is 10^?4–10^?6 m).     

Magnetic fluid in ionizing electric field

This article describes influence of strong (ionizing) electric field on sprayability of magnetic fluid containing colloid particles with size in the range from 10 to 20 nm of magnetite Fe₃O₄. Magnetic fluids can be based for example on both transformer oil and physiological solution for application in medical using (in human medical science research), that supports a fluid colloidal system. Further component of magnetic fluid is surfactant. It is acting as surface-active substance that prevents from nanometric dimension particle settlement. Magnetic fluid gets off nozzle with diameter in range 0.3–1.0 mm from container in surroundings of ionizing (i.e. strong) electric field (E > 10⁷ V m^?1). As a consequence of action of electric field it gives out suppression surface tension in fluid what leads onwards to decomposition of magnetic fluid ligament at the end of nozzle. The diameter of nozzle oneself respects basic theoretical calculations in regards of fluid concentration and thereinbefore its selected size. Magnetic fluid in dependency on its used liquid base has weak-polar till polar orientation polarization character. It gives out sprayability in non-homogeneous electric field E in combination with magnetic field of intensity H. Orientation of vectors Ê and ?, resp. induction of magnetic field B is defined by parallel or vertical direction. Results are confronted with measurements realized explicitly only at action of electric field (variable B = 0). In the case of magnetic field applications with permanent magnet together with electric non-homogeneous field it gives out unconventional dynamics of electrical charging particles of macroscopic dimension. Orientation particle track is influenced by orientation of field vector combinations. This phenomenon develops magneto-dielectric anisotropy, which oneself manifests behaviour of electrophysical quantities characterizing examination system. In consideration of technology utilization of this method it is very important to respect applied magnetic fluid concentration. Electrical characteristics were examined for volume concentration of magnetite particles in the range from 0.125% to 18%. Nevertheless efficiency optimization of given media suggests to boundary concentration of magnetic fluid of 4.0%, when it is in the regions of weak polar till polar material. Electrophysical research refers to exploitation of applied magnetic layer technology on dielectric insulating substances with inorganic origin as well as thin layer technology coating plastic foils created from macromolecular organic substance.     

Sampling the Variational Posterior with Local Refinement

Variational inference is an optimization-based method for approximating the posterior distribution of the parameters in Bayesian probabilistic models. A key challenge of variational inference is to approximate the posterior with a distribution that is computationally tractable yet sufficiently expressive. We propose a novel method for generating samples from a highly flexible variational approximation. The method starts with a coarse initial approximation and generates samples by refining it in selected, local regions. This allows the samples to capture dependencies and multi-modality in the posterior, even when these are absent from the initial approximation. We demonstrate theoretically that our method always improves the quality of the approximation (as measured by the evidence lower bound). In experiments, our method consistently outperforms recent variational inference methods in terms of log-likelihood and ELBO across three example tasks: the Eight-Schools example (an inference task in a hierarchical model), training a ResNet-20 (Bayesian inference in a large neural network), and the Mushroom task (posterior sampling in a contextual bandit problem).