Recently it has been revealed that when approaching the glass-transition temperature, T(g), the dynamics of a liquid not only drastically slows down, but also becomes progressively more heterogeneous. From our simulations and experiments of six different glass-forming liquids, we find that the heterogeneous dynamics is a result of critical-like fluctuations of static structural order, contrary to a common belief that it is purely of dynamic origin. The static correlation length and susceptibility of a structural order parameter show Ising-like power-law divergence towards the ideal glass-transition point. However, this structural ordering accompanies little density change, which explains why it has not been detected by the static structure factor so far. Our results suggest a far more direct link than thought before between glass transition and critical phenomena. Indeed, the glass transition may be a new type of critical phenomenon where a structural order parameter is directly linked to slowness.

Singlet fission, in which a singlet exciton is converted to two triplet excitons, is a process that could be beneficial in photovoltaic applications. A full understanding of the dynamics of singlet fission in molecular systems requires detailed knowledge of the relevant potential energy surfaces and their (conical) intersections. However, obtaining such information is a nontrivial task, particularly for molecular aggregates. Here we investigate singlet fission in rubrene crystals using transient absorption spectroscopy and state-of-the-art quantum chemical calculations. We observe a coherent and ultrafast singlet-fission channel as well as the well-known and conventional thermally assisted incoherent channel. This coherent channel is accessible because the conical intersection for singlet fission on the excited-state potential energy surface is located very close to the equilibrium position of the ground-state potential energy surface and also because of the excitation of an intermolecular symmetry-breaking mode, which activates the electronic coupling necessary for singlet fission.

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Collective behavior of driven granular matter is often strikingly analogous to that of thermal systems. Here we use a vibrated quasi-two-dimensional granular matter as a model system and investigate the mechanism of the liquid-glass transition. We demonstrate by direct observation the existence of long-lived medium-range crystalline order, which is found to be closely related to both dynamic heterogeneity and slow dynamics. Our findings are remarkably similar to recent numerical results on model thermal liquids and thus open an intriguing possibility of understanding the dynamic arrest in both thermal and athermal systems in a unified manner.

Spatial confinement is known to induce a drastic change in the viscosity, relaxation times, and flow profile of liquids near the glass (or jamming) transition point. The essential underlying question is how a wall affects the dynamics of densely packed systems. Here we study this fundamental problem, using experiments on a driven granular hard-sphere liquid and numerical simulations of polydisperse and bidisperse colloidal liquids. The nearly hard-core nature of the particle-wall interaction provides an ideal opportunity to study purely geometrical confinement effects. We reveal that the slower dynamics near a wall is induced by wall-induced enhancement of 'glassy structural order', which is a manifestation of strong interparticle correlations. By generalizing the structure-dynamics relation for bulk systems, we find a quantitative relation between the structural relaxation time at a certain distance from a wall and the correlation length of glassy structural order there. Our finding suggests that glassy structural ordering may be the origin of the slow glassy dynamics of a supercooled liquid.

The performance of current Li–air batteries is greatly limited by critical obstacles such as electrolyte decomposition, high charging overpotentials, and limited cycle life. Thus, much effort is devoted to fundamental studies to understand the mechanisms of discharge/charge processes and overcome the above-mentioned obstacles. In particular, the search for new stable electrolytes is vital for long-lasting and highly cyclable batteries. The highly reactive lithium superoxide intermediate (LiO2) produced during discharge process can react with the electrolyte and produce a variety of byproducts that will shorten battery life span. To study this degradation mechanism, we investigated oxygen reduction reaction (ORR) in highly concentrated electrolyte solutions of lithium bis­(trifluoromethanesulfonyl)­amide (Li­[TFSA])/dimethyl sulfoxide (DMSO). On the basis of rotating ring disk electrode measurements, we showed that LiO2 dissolution can be limited by increasing lithium salt concentration over 2.3 mol dm–3. Our Raman results suggested that this phenomenon can be related to lack of free DMSO molecules and increasing DMSO–Li+ interactions with higher Li+ concentration. X-ray diffraction measurements for the products of ORR suggested that the side reaction of DMSO with Li2O2 and/or LiO2 could be suppressed by decreasing the solubility of LiO2 in highly concentrated electrolytes.

A set of flapping acene dimers fused with an 8π cyclooctatetraene (COT) ring showed distinct excited-state dynamics in solution. While the anthracene dimer showed a fast V-shaped-to-planar conformational change within 10 ps in the lowest excited singlet state, reminding us of extended Baird aromaticity, the tetracene dimer and the pentacene dimer underwent intramolecular singlet fission (SF) in different manners: A fast and reversible SF with a characteristic delayed fluorescence (FL), and a fast and quantitative SF, respectively. Conformational flexibility of the fused COT linkage plays an important role in these ultrafast dynamics, demonstrating the utility of the flapping molecular series as a versatile platform for designing photofunctional systems.

The role of copper Damascene additives is discussed based on electrodeposit morphology on a through-mask cathode, field emission-Auger ͑FE-Auger͒, quartz crystal microbalance ͑QCM͒, and electrochemical measurements. Adsorbed particles, several tens of nanometers in diameter were observed on copper-electrodeposited surfaces by field emission-scanning electron microscopy ͑FE-SEM͒. These particles show a stronger oxygen intensity peak by FE-Auger spectrum than bare electrodeposited surfaces. The QCM frequency deviation did not increase with time in the CuSO 4 and H 2 SO 4 bath without polyethylene glycol ͑PEG͒ and chloride ion (Cl Ϫ) additives. When the substrates were immersed in the bath with these additives, the deviation markedly increased with time. Numerous PEG molecules were observed by FE-SEM immersed after 1000 s. The current density remained constant at a low value for the bath with PEG and Cl Ϫ additives. The current density started to increase markedly with time just after adding 1 ppm of bis͑3-sulfopropyl͒ disulfide ͑SPS͒. Numerous PEG molecules were present on the electrodeposits before adding SPS. No PEG molecules, however, remained on the surface once SPS was added to the bath. The current density increased with narrower opening widths of the through-mask cathode. Despite this increase, the deposit cross sections on narrower opening widths of 2 and 10 m were flat and no curvatures were found. Hence, the deposit curvature is not the origin of the acceleration effect.