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By use of an analytic potential energy surface developed in this work for nitric acid, the quasi-classical trajectory method was used to simulate intramolecular vibrational energy redistribution (IVR). A method was developed for monitoring the average vibrational energy in the OH (or OD) mode that uses the mean-square displacement of the bond length calculated during the trajectories. This method is effective for both rotating and nonrotating molecules. The calculated IVR time constant for HONO(2) decreases exponentially with increasing excitation energy, is almost independent of rotational temperature, and is in excellent agreement with the experimental determination (Bingemann, D.; Gorman, M. P.; King, A. M.; Crim, F. F. J. Chem.Phys. 1997, 107, 661). In DONO(2), the IVR time constants show more complicated behavior with increasing excitation energy, apparently due to 2:1 Fermi-resonance coupling with lower frequency modes. This effect should be measurable in experiments.

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To disentangle the factors controlling the rates of accelerated reactions in droplets, we used mass spectrometry to study the Katritzky transamination in levitated Leidenfrost droplets of different yet constant volumes over a range of concentrations while holding concentration constant by adding back the evaporated solvent. The set of concentration and droplet volume data indicates that the reaction rate in the surface region is much higher than that in the interior. These same effects of concentration and volume were also seen in bulk solutions. Three pyrylium reagents with different surface activity showed differences in transamination reactivity. The conclusion is drawn that reactions with surface-active reactants are subject to greater acceleration, as seen particularly at lower concentrations in systems of higher surface-to-volume ratios. These results highlight the key role that air-solution interfaces play in Katritzky reaction acceleration. They are also consistent with the view that reaction-increased rate constant is at least in part due to limited solvation of reagents at the interface.

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Magnesium hydride has long been regarded as a promising candidate material for hydrogen and heat storage due to its high hydrogen capacity, reversibility, and low cost. Catalytic doping has been demonstrated as one of the most effective methods to improve hydrogen storage properties of MgH2. In this study, amorphous Ti45Cu41Ni9Zr5 and Ti40Cu47Zr10Sn3 alloys are used as additives for MgH2. Nanostructured MgH2 doped with amorphous or crystalline TiCu-based alloys are prepared by using a high-energy mechanochemical synthesis method. Results show that the amorphous TiCu additives provide enhanced catalytic effects compared to crystalline alloys of the same composition. Doping MgH2 using an amorphous Ti45Cu41Ni9Zr5 alloy yielded improved dehydrogenation kinetics compared to using crystalline Ti40Cu47Zr10Sn3 alloy. The analysis using transmission electron microscopy reveals that there are nanostructured catalytic particles uniformly distributed in the amorphous TiCu-catalyzed MgH2. The MgH2 system catalyzed by amorphous TiCu-based alloy shows little degradation during hydrogenation and dehydrogenation cycling at 300 °C. The amorphous TiCu-based catalysts are thermally stable at temperatures up to 360 °C. Heating the amorphous Ti45Cu41Ni9Zr5-catalyzed MgH2 to temperatures above 360 °C led to disproportionation of the catalyst alloy and the formation of MgCu2 and Ti2Cu. In addition, PCI analysis of the amorphous Ti45Cu41Ni9Zr5-catalyzed MgH2 shows a slight increase in hydrogen equilibrium pressure, resulting in a reaction enthalpy of −78.7 kJ/mol·H2 and an entropy of 145.0 J/K·mol·H2. The entropy calculated from this study is approximately 10 J/K·mol·H2 higher than values previously reported for undoped and catalyzed Mg–H systems.

This study investigated the mechanical and shape recovery properties of a styrene-based shape memory polymer composite reinforced by cup-stacked carbon nanotubes. Due to their unique morphology, cup-stacked carbon nanotubes could be well dispersed in the polymer matrix and offer remarkable benefits in the load transfer between the reinforcement fillers and shape memory polymer. Under the same amount of fillers, shape memory polymer composites embedded with cup-stacked carbon nanotubes exhibit superior mechanical properties in comparison with those embedded with multiwalled carbon nanotubes and carbon nanofibers. The elastic modulus, tensile strength, and flexural strength of the 2 wt% cup-stacked carbon nanotube–reinforced shape memory polymer composite increased by 61%, 66%, and 84%, respectively. It was also found that the glass transition temperature of shape memory polymer composite decreased from 61.9°C to 52.8°C by introducing 2 wt% cup-stacked carbon nanotubes, indicating that the shape recovery process could be triggered more easily by external stimulus due to the role of reinforcement fillers. Finally, under the external resistance load, the developed shape memory polymer composite was successfully driven to recover their shapes under thermal stimulus. The cup-stacked carbon nanotubes were proved to be a promising candidate for the polymer reinforcement.