Vibrationally excited molecular hydrogen has been commonly observed in the dense photo-dominated regions (PDRs). It plays an important role in understanding the chemical evolution in the interstellar medium. Until recently, it was widely accepted that vibrational excitation of interstellar H2 was achieved by shock wave or far-ultraviolet fluorescence pumping. Here we show a further pathway to produce vibrationally excited H2 via the water photochemistry. The results indicate that the H2 fragments identified in the O(1S) + H2(X1Σg+) channel following vacuum ultraviolet (VUV) photodissociation of H2O in the wavelength range of λ = ~100-112 nm are vibrationally excited. In particular, more than 90% of H2(X) fragments populate in a vibrational state v = 3 at λ~112.81 nm. The abundance of water and VUV photons in the interstellar space suggests that the contributions of these vibrationally excited H2 from the water photochemistry could be significant and should be recognized in appropriate interstellar chemistry models.
The water octamer with its cubic structure consisting of six four-membered rings presents an excellent cluster system for unraveling the cooperative interactions driven by subtle changes in the hydrogen-bonding topology. Despite prediction of many distinct structures, it has not been possible to extract the structural information encoded in their vibrational spectra because this requires size-selectivity of the neutral clusters with sufficient resolution to identify the contributions of the different isomeric forms. Here we report the size-specific infrared spectra of the isolated cold, neutral water octamer using a scheme based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. A plethora of sharp vibrational bands features are observed. Theoretical analysis of these patterns reveals the coexistence of five cubic isomers, including two with chirality. The relative energies of these structures are found to reflect topology-dependent, delocalized multi-center hydrogen-bonding interactions. These results demonstrate that even with a common structural motif, the degree of cooperativity among the hydrogen-bonding network creates a hierarchy of distinct species. The implications of these results on possible metastable forms of ice are speculated.
Abstract Double-shelled Au/Ag hollow nanoboxes with precisely controlled interior nanogaps (1 to 16 nm) were synthesized for gap-tunable surface-enhanced Raman scattering (SERS). The double-shelled nanoboxes were prepared via a two-step galvanic replacement reaction approach using Ag nanocubes as the templates, while 4-aminothiolphenol (4-ATP) as SERS probe molecules were loaded between the two shells. More than 10-fold enhancement of SERS is observed from the double-shelled nanoboxes than Ag nanocubes. In addition, the SERS of the double-shelled nanoboxes increase significantly with the decrease of gap size, consistent with the theoretical prediction that smaller gap size induces larger localized electromagnetic enhancement.
Abstract A coupled atmosphere–wave–sea spray model system is used to evaluate the combined impacts of spray evaporation and wave drag on midlatitude storms. The focus of this paper is on the role of air–sea fluxes on storm intensity and development, and related impacts on the structure of the atmospheric boundary layer. The composite model system consists of the Canadian Mesoscale Compressible Community atmospheric model coupled to the operational wave model WAVEWATCH III, and a recent bulk parameterization for heat fluxes due to sea spray. The case studies are extratropical Hurricane Earl (in 1998) and two intense winter storms from 2000 and 2002, hereafter denoted “superbomb” and “bomb,” respectively. The results show that sea spray tends to intensify storms, whereas wave-related drag tends to weaken storms. The mechanisms by which spray and wave-related drag can influence storm intensity are quite different. When wind speeds are high and sea surface temperatures warm, spray can significantly increase the surface heat fluxes. By comparison, momentum fluxes related to wave drag are important over regions of the storm where young, newly generated waves are prevalent, for example during the rapid development phase of the storm. These momentum fluxes decrease in areas where the storm waves reach maturity. The collective influence of spray and waves on storm intensity depends on their occurrence in the early stages of a storm’s rapid intensification phase, and their spatial distribution with respect to the storm center. Moreover, for the case of the superbomb, a potential vorticity framework is used to show the relative importance of these surface flux impacts compared with baroclinic processes.
Abstract The direct conversion of low alkane such as ethane into high-value-added chemicals has remained a great challenge since the development of natural gas utilization. Herein, we achieve an efficient one-step conversion of ethane to C 2 oxygenates on a Rh 1 /AC-SNI catalyst under a mild condition, which delivers a turnover frequency as high as 158.5 h −1 . 18 O isotope-GC–MS shows that the formation of ethanol and acetaldehyde follows two distinct pathways, where oxygen and water directly participate in the formation of ethanol and acetaldehyde, respectively. In situ formed intermediate species of oxygen radicals, hydroxyl radicals, vinyl groups, and ethyl groups are captured by laser desorption ionization/time of flight mass spectrometer. Density functional theory calculation shows that the activation barrier of the rate-determining step for acetaldehyde formation is much lower than that of ethanol, leading to the higher selectivity of acetaldehyde in all the products.
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