High Internal Energy Research Articles

Epitaxial Growth of Twinned Au-Pt Core-Shell Star-Shaped Decahedra as Highly Durable Electrocatalysts.

Pt epitaxial layer on a nanoparticle with twinned structure and well-defined shape is highly desirable in order to achieve high performance in both catalytic activity and durability toward oxygen reduction reaction (ORR). However, it remains tremendously challenging to produce conformal, heterogeneous, twinned nanostructures due to the high internal strain and surface energy of Pt. In addition, these twinned nanostructures may be subject to degradation in highly corrosive ORR environments due to the high energy of twin boundary. Here we report the synthesis of Au-Pt core-shell star-shaped decahedra bounded mainly by {111} facets, in which Pt shells with controlled thickness epitaxially grew on Au cores with a 5-fold twinned structure. The incorporation of the amine group decreases the surface energy of Pt by strong adsorption and thus facilitates the epitaxial growth of Pt on Au core instead of the dendritic growth. In addition, Br(-) ion could largely stabilize the {111} facets of Pt, which prevent the formation of spherical nanoparticles. The Au-Pt core-shell decahedra with thicker Pt shell exhibited enhanced ORR properties in terms of activity and durability. Specifically, AuPt1.03 star-shaped decahedra achieved the highest mass activity (0.94 mA/μg(Pt)) and area activity (1.09 mA/cm(2)(Pt)), which is ∼6.7 and 5 times, respectively, as high as those of the commercial Pt/C (ETEK). Significantly, such star-shaped decahedra were highly stable with ∼10% loss in area activity and ∼20% loss in mass activity after 30,000 CV cycles in O2 saturated acid solution.

Dissociative Photoionization of Diethyl Ether.

The dissociative photoionization of internal energy selected diethyl ether ions was investigated by imaging photoelectron photoion coincidence spectroscopy. In a large, 5 eV energy range Et2O(+) cations decay by two parallel and three sequential dissociative photoionization channels, which can be modeled well using statistical theory. The 0 K appearance energies of the CH3CHOCH2CH3(+) (H-loss, m/z = 73) and CH3CH2O═CH2(+) (methyl-loss, m/z = 59) fragment ions were determined to be 10.419 ± 0.015 and 10.484 ± 0.008 eV, respectively. The reemergence of the hydrogen-loss ion above 11 eV is attributed to transition-state (TS) switching, in which the second, outer TS is rate-determining at high internal energies. At 11.81 ± 0.05 eV, a secondary fragment of the CH3CHOCH2CH3(+) (m/z = 73) ion, protonated acetaldehyde, CH3CH═OH(+) (m/z = 45) appears. On the basis of the known thermochemical onset of this fragment, a reverse barrier of 325 meV was found. Two more sequential dissociation reactions were examined, namely, ethylene and formaldehyde losses from the methyl-loss daughter ion. The 0 K appearance energies of 11.85 ± 0.07 and 12.20 ± 0.08 eV, respectively, indicate no reverse barrier in these processes. The statistical model of the dissociative photoionization can also be used to predict the fractional ion abundances in threshold photoionization at large temperatures, which could be of use in, for example, combustion diagnostics.

CRASH ANALYSIS OF RACING CAR NOSE CONE SUBJECTED TO FULL FRONTAL IMPACT

Racing a car involves high-speed and having high possibility to crash either among the racer or hitting the bench. Concerning the driver safety, impact structures such as nose cone is designed to absorb the race car kinetic energy to limit the decelerations acting on the human body. In this study, analysis of different type of nose cone material were conducted. The objective is to find the highest specific energy absorption (SEA) based on three different materials which are mild steel, aluminium and composite material. The nose cone was modelled using CATIA V5R16 while the crash simulation was done using LS-DYNA and LS-Prepost software with an average velocity of 80km/hour according to United States New Car Assessment Program (US-NCAP) frontal impact velocity and based on European Enhanced Vehicle-safety Committee. The simulation results show that fiberglass E with thickness of 2.6 mm and lay-up configurations of [0°/30°/60°/90°/120°] give the highest internal energy and specific energy absorption of 41.28845 kJ and 6.9104 kJ/kg. This concludes that fiberglass E is a suitable material to build a lightweight structure compared to steel and aluminium.

Mechanical alloying and thermal analysis of Ta–Ti alloys

Tantalum–titanium alloys have widespread potential in biomedical applications due to their superior biocompatibility, favorable mechanical properties, high corrosion resistance, and ability to exhibit shape memory behavior. However, this system is plagued by processing difficulties due to significant differences in melting temperatures, specific weights, and vapor pressures of Ta and Ti. In the present study, mechanical alloying (MA) using high‐energy ball milling of Ti–xTa (where x = 50, 60, 70, and 85 wt%) was investigated. The alloyed powders were characterized by X-ray diffraction, electron microscopy (SEM and TEM), and differential scanning calorimetry. It was established that α-Ti (hcp) gradually dissolves into α-Ta (bcc), with the alloyed particles becoming chemically homogeneous as a bcc structure. This structure corresponds to a meta-stable phase and should decompose to yield two solid solutions, Ti-rich hcp and Ta-rich bcc. To overcome this thermodynamic preference, MA-generated Ta–Ti bcc solid solution powders possess relatively high internal strain energy.

Top-down formation of fullerenes in the interstellar medium.

Fullerenes have been recently detected in various circumstellar and interstellar environments, raising the question of their formation pathway. It has been proposed that they can form at the low densities found in the interstellar medium by the photo-chemical processing of large polycyclic aromatic hydrocarbons (PAHs). Following our previous work on the evolution of PAHs in the NGC 7023 reflection nebula, we evaluate, using photochemical modeling, the possibility that the PAH C66H20 (i.e. circumovalene) can lead to the formation of C60 upon irradiation by ultraviolet photons. The chemical pathway involves full dehydrogenation of C66H20, folding into a floppy closed cage and shrinking of the cage by loss of C2 units until it reaches the symmetric C60 molecule. At 10" from the illuminating star and with realistic molecular parameters, the model predicts that 100% of C66H20 is converted into C60 in ~ 105 years, a timescale comparable to the age of the nebula. Shrinking appears to be the kinetically limiting step of the whole process. Hence, PAHs larger than C66H20 are unlikely to contribute significantly to the formation of C60, while PAHs containing between 60 and 66 C atoms should contribute to the formation of C60 with shorter timescales, and PAHs containing less than 60 C atoms will be destroyed. Assuming a classical size distribution for the PAH precursors, our model predicts absolute abundances of C60 are up to several 10-4 of the elemental carbon, i.e. less than a percent of the typical interstellar PAH abundance, which is consistent with observational studies. According to our model, once formed, C60 can survive much longer (> 107 years for radiation fields below G0 = 104) than other fullerenes because of the remarkable stability of the C60 molecule at high internal energies. Hence, a natural consequence is that C60 is more abundant than other fullerenes in highly irradiated environments.

Nitrogen-atom endohedral fullerene synthesis with high efficiency by controlling plasma-ion irradiation energy and C60 internal energy

The nitrogen-atom endohedral fullerene (N@C60) has been synthesized by controlling the plasma ion irradiation energy (Ei) and fullerene (C60) behavior in the sublimation phase. We examined the relationship between the synthesis purity of N@C60 [molar concentration ratio of N@C60 to pristine fullerene (C60)] and Ei, which was controlled by changing the substrate bias voltages (Vsub) and gas pressure (PN2) during the plasma irradiation process. High-density nitrogen-molecular ions (N2+) with a suitable Ei near 80 eV are confirmed to be the optimum condition of the nitrogen plasma for the synthesis of high-purity N@C60. In addition, high sublimation of C60 contributes to a higher yield due to the high internal energy of C60 and the related cage defects that are present under these conditions. As a result, a purity of 0.83% is realized for the first time, which is almost two orders of magnitude higher than that using other methods.

On the interactions between nucleotide binding domains and membrane spanning domains in cystic fibrosis transmembrane regulator: A molecular dynamic study.

The Cystic Fibrosis Transmembrane Regulator (CFTR) is a membrane protein whose mutations cause cystic fibrosis, a lethal genetic disease. We performed a molecular dynamic (MD) study of the properties of the nucleotide binding domains (NBD) whose conformational changes, upon ATP binding, are the direct responsible of the gating mechanisms of CFTR. This study was done for the wild type (WT) CFTR and for the two most common mutations, ΔF508, that produces a traffic defect of the protein, and the mutation G551D, that causes a gating defect on CFTR. Using an homology model of the open channel conformation of the CFTR we thus introduced the mutations to the structure. Although the overall structures of the G551D and ΔF508 are quite well conserved, the NBD1-NBD2 interactions are severely modified in both mutants. NBD1 and NBD2 are indeed destabilized with a higher internal energy (Ei) in the ΔF508-CFTR. Differently, Ei does not change in the NBDs of G551D but, while the number of close contacts between NBD1 and NBD2 in ΔF508 is increased, a significant reduction of close contacts is found in the G551D mutated form. Hydrogen bonds formation between NBDs of the two mutated forms is also altered and it is slightly increased for the ΔF508, while are severely reduced in G551D. A consequent modification of the NBDs-ICLs interactions between residues involved in the transduction of the ATP binding and the channel gating is also registered. Indeed, while a major interaction is noticed between NBDs interface and ICL2 and ICL4 in the WT, this interaction is somehow altered in both mutated forms plausibly with effect on channel gating. Thus, single point mutations of the CFTR protein can reasonably results in channel gating defects due to alteration of the interaction mechanisms between the NBDs and NBDs-ICLs interfaces upon ATP-binding process.

Highly strained nonclassical nanotube end-caps. A single-step solution synthesis from strain-free, non-macrocyclic precursors.

Nonclassical nanotube end-caps have been constructed from strain-free heterocyclic precursors using a one-step synthetic procedure, involving multiple nickel-mediated Ullmann couplings. These systems consist of tubular macrocyclic sections that are tightly capped on one side with a bridging benzene ring, forming deep, chemically accessible cavities. The end-caps are characterized by exceptionally high internal strain energies reaching 144 kcal/mol. The optical absorption and emission properties of these molecules show a marked dependence on conjugation length and geometrical factors. The mechanism of end-cap formation, investigated using DFT calculations, relies on precise timing of transmetalation and reductive elimination events.

Simulation-based Study of Layered Aluminum Crystal Microstructures Subjected to Shock Loading

A one-dimensional finite difference method allowing for anisotropic deformation is used in conjunction with a nonlinear thermoelastic-viscoplastic material model to compute the shock response of various microstructural instantiations of pure aluminum at peak stresses exceeding the Hugoniot Elastic Limit (HEL). Single crystals and layered bi-materials consisting of grains with alternating orientations relative to the direction of shock propagation -- specifically [100], [111], or low-symmetry orientations -- are impacted to peak shock stresses on the order of 5GPa. The [111] orientation [111] is observed to be stiffest both plastically and elastically, while the [100] orientation is found to be most compliant. Layered bi-materials that only demonstrate pure longitudinal waves exhibit average shock stresses, entropy production, and internal energy in between values computed for their single crystal constituents. Layered bi-materials that generate both quasi-longitudinal and quasi-transverse waves results in lower peak stresses and higher internal energy than their single crystal constituents. In bi-material systems, stress fluctuations decrease in frequency with increasing layer thickness, and peak stress amplitudes increase with layer thickness. Average dissipation depends on orientation but is relatively insensitive to layer thickness. Results of the computational method may ultimately be used to guide design of metallic systems with microstructures tailored for optimal impact resistance.

Design of Transformer-Based Boost Converter for High Internal Resistance Energy Harvesting Sources With 21 mV Self-Startup Voltage and 74% Power Efficiency

Thin-film thermoelectric generators (TEG) or graphene-based microbial fuel cells (MFC) are emerging energy harvesting sources with promising power density and sustainability. Nevertheless, conventional transformer-based boost converters commonly used to achieve autonomous low voltage startup encounter low efficiency and potential startup problems with these novel power sources due to their high internal resistance. In this paper, an improved design of transformer-based boost converter addressing these issues is demonstrated with prototype chip fabricated using a standard 0.13 μm CMOS process. The self-start oscillation does not rely on the conventional LC resonant principle, but instead is dependent on the MOS transistor's active-over-leakage current ratio and the mutual coupling between the two identical transformer coils. Circuit design techniques to regulate output voltage and to track system's maximum power point (MPP) of this boost converter are presented. Measurement results confirmed that the proposed circuit works with either low threshold voltage or native MOS transistors. It needs minimum self-startup voltage of 21 mV (at 5.8 μW input power) and minimum startup power of 1.3 μW (at 35 mV input voltage) respectively. The maximum output power is 2 mW and peak power conversion efficiency is 74% at a regulated output voltage of 1 V.

Effect of non-thermal product energy distributions on ketohydroperoxide decomposition kinetics

The decomposition of ketohydroperoxides (OQ′OOH) to two radicals is commonly predicted to be the key chain branching step in low-temperature combustion. The possibility of a direct decomposition of the OQ′OOH from its initially produced energy distribution is studied with a combination of master equation (ME) and direct trajectory simulations. The temperature and pressure dependent rate constants for the thermal decomposition of a ketohydroperoxide, HOOCH2CH2CHO, to four product channels were computed using RRKM/ME methods. Direct dynamics calculations were initiated from a transition state in the O2+QOOH reaction network to understand the fraction of energy in that transition state that is converted into the internal energy of the OQ′OOH. A novel approach to solving the master equation is used to determine the probability that a vibrationally hot OQ′OOH either will be stabilized to a thermal distribution or will react to form new products. Under most conditions, the majority of vibrationally excited OQ′OOH will be quenched into a thermal distribution. At higher internal energies and lower pressures, however, a significant fraction of the hot OQ′OOH will decompose rather than thermalize. Proper interpretation of low-pressure experiments may require inclusion of vibrationally hot intermediates, particularly if a chemical kinetic mechanism is optimized against the low-pressure data.

Shock compressibility of high-porosity copper and tin powders

The particle and wave velocities in copper and tin samples with an extremely high porosity are measured by a magnetoelectric method. Relations between the wave and particle velocities are obtained for copper with a density of 0.76 and 0.54 g/cm3 (porosity factor of 12 and 16, respectively) and for tin with a density of 1.9 g/cm3 (porosity factor of 3.9). The obtained data are used to find other hydrodynamic parameters of a compressed substance (density, pressure, specific internal energy) using the laws of conservation. The parameters of the state of copper and tin are found in the region of the P-V-T states of the metals that has not been studied earlier and corresponds to low densities and high internal energies.

Ab initio study of Fermi surface and dynamical properties of Ni2XAl (X = Ti, V, Zr, Nb, Hf and Ta)

A detailed study on the pressure and temperature effects on ternary Ni-based inter-metallic compounds Ni2XAl (X=Ti, V, Zr, Nb, Hf and Ta) have been carried out using density functional theory. The calculated ground state properties are in good agreement with experiments for all the investigated compounds. The band structures and Fermi surface topology is found to be quite similar for all the compounds except for Ni2NbAl, where we find an extra band to cross the Fermi level under compression resulting in a new electron pocket at X-point. Ni2NbAl is found to be a superconductor with superconducting transition temperature of 3.1K which agrees quite well with the experimental value and the calculated Tc is found to vary non-monotonically under pressure. From the calculated phonon dispersion relation, we find all the investigated Ni-based Heusler compounds to be dynamically stable, until high pressure. The ductile nature of these compounds is confirmed from the calculated Cauchy’s pressure, Pugh’s ratio and Poisson’s ratio. In addition, the thermodynamic properties show Ni2TiAl to have lower specific heat and entropy but higher internal energy and free energy among all the investigated compounds.

Further studies into the photodissociation pathways of 2-bromo-2-nitropropane and the dissociation channels of the 2-nitro-2-propyl radical intermediate.

These experiments investigate the decomposition mechanisms of geminal dinitro energetic materials by photolytically generating two key intermediates: 2-nitropropene and 2-nitro-2-propyl radicals. To characterize the unimolecular dissociation of each intermediate, we form them under collision-free conditions using the photodissociation of 2-bromo-2-nitropropane; the intermediates are formed at high internal energies and undergo a multitude of subsequent unimolecular dissociation events investigated herein. Complementing our prior work on this system, the new data obtained with a crossed-laser molecular beam scattering apparatus with VUV photoionization detection at Taiwan's National Synchrotron Radiation Research Center (NSRRC) and new velocity map imaging data better characterize two of the four primary 193 nm photodissociation channels. The C-Br photofission channel forming the 2-nitro-2-propyl radicals has a trimodal recoil kinetic energy distribution, P(ET), suggesting that the 2-nitro-2-propyl radicals are formed both in the ground electronic state and in two low-lying excited electronic states. The new data also revise the HBr photoelimination P(ET) forming the 2-nitropropene intermediate. We then resolved the multiple competing unimolecular dissociation channels of each photoproduct, confirming many of the channels detected in the prior study, but not all. The new data detected HONO product at m/e = 47 using 11.3 eV photoionization from both intermediates; analysis of the momentum-matched products allows us to establish that both 2-nitro-2-propyl → HONO + CH3CCH2 and 2-nitropropene → HONO + C3H4 occur. Photoionization at 9.5 eV allowed us to detect the mass 71 coproduct formed in OH loss from 2-nitro-2-propyl; a channel missed in our prior study. The dynamics of the highly exothermic 2-nitro-2-propyl → NO + acetone dissociation is also better characterized; it evidences a sideways scattered angular distribution. The detection of some stable 2-nitropropene photoproducts allows us to fit signal previously assigned to H loss from 2-nitro-2-propyl radicals. Overall, the data provide a comprehensive study of the unimolecular dissociation channels of these important nitro-containing intermediates.

Reaction dynamics of Al + O₂ → AlO + O studied by a crossed-beam velocity map imaging technique: vib-rotational state selected angular-kinetic energy distribution.

Oxidation reaction of a gas-phase aluminum atom by a molecular oxygen was studied by a crossed-beam condition at 12.4 kJ/mol of collision energy. A (1+1) resonance-enhanced multiphoton ionization (REMPI) via the D(2)Σ(+)-X(2)Σ(+) transition of AlO was applied to ionize the product. The REMPI spectrum was analyzed to determine rotational state distributions for v = 0-2 of AlO. For several vib-rotational states of AlO, state selected angular and kinetic energy distributions were determined by a time-sliced ion imaging technique for the first time. Kinetic energy distributions were well represented by that taken into account initial energy spreads of collision energy and the population of the spin-orbit levels of the counter product O((3)P(J)) determined previously. All angular distributions showed forward and backward peaks, and the forward peaks were more pronounced than the backward one for the states of low internal energy. The backward peak intensity became comparable to the forward one for the states of high internal energy. These results and the rotational state distributions suggested that the reaction proceeds via an intermediate which has a lifetime comparable to or shorter than its rotational period.

Carbon dioxide ion dissociations after inner shell excitation and ionization: the origin of site-specific effects.

Multi-coincidence experiments with detection of both electrons and ions from decay of core-excited and core-ionized states of CO2 confirm that O2(+) is formed specifically in Auger decay from the C1s-π* and O1s-π* resonances. Molecular rearrangement occurs by bending in the resonant states, and O2(+) is produced by both single and double Auger decay. It is suggested that electron capture by C(+) after partial dissociation in the doubly ionized core of excited CO2(+), formed by shake-up in spectator resonant Auger decay, accounts for high kinetic energy and high internal energy in some C + O2(+) fragments.

Vibrational spectroscopy of the water-nitrate complex in the O-H stretching region.

The vibrational spectroscopy of the nitrate-water isotopologues is studied in the O-H and O-D stretching regions using temperature-dependent infrared multiple photon dissociation spectroscopy combined with calculations of the anharmonic spectra. At a temperature of 15 K a series of discrete peaks is observed in the IRMPD spectra of NO3(-)·H2O, NO3(-)·HDO, and NO3(-)·D2O. This structure is considerably more complex than predicted by harmonic calculations. A signal is only observed in the hydrogen-bonded O-H (O-D) stretching region, characteristic of a double hydrogen-bond donor binding motif. With increasing temperature, the peaks broaden, leading to a quasi-continuous absorption from 3150 to 3600 cm(-1) (2300-2700 cm(-1)) for NO3(-)·H2O (NO3(-)·D2O) and, above 100 K, an additional band in the free O-H (O-D) stretching region, suggesting the population of complexes containing only a single hydrogen bond at higher internal energies. Vibrational configuration interaction calculations confirm that much of the structure observed in the IRMPD spectra derives from progressions in the water rocking mode resulting from strong cubic coupling between the O-H (O-D) stretch and water rock degrees of freedom. The spectra of both NO3(-)·H2O and NO3(-)·D2O display a strong peak that does not derive from the water rock progression but results instead from a Fermi resonance between the O-H (O-D) stretch and H-O-H (D-O-D) bend overtone. Additional insight into the nature of the O-H (O-D) stretch and water rocking coupling in these complexes is provided by an effective Hamiltonian that allows for the cubic coupling between the O-H stretch and water rock degrees of freedom.

Time evolution of internal energy distribution of Anthracene studied in an electrostatic storage ring, the Mini-Ring

Fast radiative cooling of polycyclic aromatic hydrocarbon (PAH) was studied by probing the time evolution of the internal energy distribution of hot molecular ensembles in the ms range. Anthracene cations (C14H10)+ prepared in an electron cyclotron resonance ion source were stored in an electrostatic storage ring, the Mini-Ring [1]. The experiment showed that in the first milliseconds, the time evolution of the stored ion population distribution was dominated by the unimolecular dissociation of the molecular ions with higher internal energy. Then, in the next milliseconds, the unimolecular dissociation was quenched by radiative cooling. In a larger time range, from 4 to 8 ms, the time evolution of the internal energy distribution was probed by reheating a part of the molecular ensemble by laser photon absorption at different storage times. We report here the measurement of a fast radiative cooling rate (100s−1) that can't be explained by vibrational IR emission but rather by electronic fluorescence from thermally excited electronic states [2].

Energy- and Time-Dependent Branching to Competing Paths in Coupled Unimolecular Dissociations of Chlorotoluene Radical Cations

The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to C7H7 + (benzylium and tropylium). There are four different paths to C7H7 + , three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to C7H7 + is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

Photoionization spectroscopy of nucleobases and analogues in the gas phase using synchrotron radiation as excitation light source.

We review here the photoionization and photoelectron spectroscopy of the gas phase nucleic acid bases adenine, thymine, uracil, cytosine, and guanine, as well as the three base analogues 2-hydroxyisoquinoline, 2-pyridone, and δ-valerolactam in the vacuum ultraviolet (VUV) spectral regime. The chapter focuses on experimental work performed with VUV synchrotron radiation and related ab initio quantum chemical calculations of higher excited states beyond the ionization energy. After a general part, where experimental and theoretical techniques are described in detail, key results are presented by order of growing complexity in the spectra of the molecules. Here we concentrate on (1) the accurate determination of ionization energies of isolated gas phase NABs and investigation of the vibrational structure of involved ionic states, including their mutual vibronic couplings, (2) the treatment of tautomerism after photoionization, in competition with other intramolecular processes, (3) the study of fragmentation of these molecular systems at low and high internal energies, and (4) the study of the evolution of the covalent character of hydrogen bonding upon substitution, i.e., examination of electronic effects (acceptor, donor, etc.).