Fakultät II - Maschinenbau und Bioverfahrenstechnik
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We describe an experimental approach to the determination of the nascent internal state distribution of gas-phase products of a gas–liquid interfacial reaction. The system chosen for study is O(³P) atoms with the surface of liquid deuterated squalane, a partially branched long-chain saturated hydrocarbon, C₃₀D₆₂. The nascent OD products are detected by laser-induced fluorescence. Both OD (v′=0) and (v′=1) were observed in significant yield. The rotational distributions in both vibrational levels are essentially the same, and are characteristic of a Boltzmann distribution at a temperature close to that of the liquid surface. This contrasts with the distributions in the corresponding homogeneous gas-phase reactions. We propose a preliminary interpretation in terms of a dominant trapping-desorption mechanism, in which the OD molecules are retained at the surface sufficiently long to cause rotational equilibration but not complete vibrational relaxation. The significant yield of vibrationally excited OD also suggests that the surface is not composed entirely of –CD₃ endgroups, but that secondary and/or tertiary units along the backbone are exposed.
Energy- and angle-resolved photofragment distributions for ground-state Cl (²P₃/₂) and spin–orbit excited Cl* (²P₁/₂) have been recorded using the velocity map imaging technique after photodissociation of chloroform at wavelengths of 193 and ∼235 nm. Translational energy distributions are rather broad and peak between 0.6 and 1.0 eV. The spin–orbit branching ratios [Cl*]/[Cl] are 1 and 0.3 at 193 and 235 nm, respectively, indicating the involvement of two or more excited state surfaces. Considering the anisotropy parameters and branching ratios collectively, we conclude that the reaction at 193 nm takes place predominantly on the ¹Q₁ surface, while the ³Q₁ surface gains importance at lower dissociation energies around 235 nm.
We have combined the velocity map imaging technique with time-of-flight measurements to study the surface photochemistry of KBr single crystals. This approach yields 3-dimensional velocity distributions of Br atoms resulting from 193 nm photodesorption. The velocity distributions indicate that at least two non-thermal mechanisms contribute to the photodesorption dynamics. Our experimental geometry also allows us to measure the Br(²P₃⁄₂):Br(²P₁⁄₂) branching ratio, which is found to be 24:1.
The effects of surface temperature on the gas-liquid interfacial reaction dynamics of O(³P)+squalane
(2005)
OH/OD product state distributions arising from the reaction of gas-phase O(³P) atoms at the surface of the liquid hydrocarbon squalane C₃₀H₆₂/C₃₀D₆₂ have been measured. The O(³P) atoms were generated by 355 nm laser photolysis of NO₂ at a low pressure above the continually refreshed liquid. It has been shown unambiguously that the hydroxyl radicals detected by laser-induced fluorescence originate from the squalane surface. The gas-phase OH/OD rotational populations are found to be partially sensitive to the liquid temperature, but do not adapt to it completely. In addition, rotational temperatures for OH/OD(v′=1) are consistently colder (by 34±5 K) than those for OH/OD(v′=0). This is reminiscent of, but less pronounced than, a similar effect in the well-studied homogeneous gas-phase reaction of O(³P) with smaller hydrocarbons. We conclude that the rotational distributions are composed of two different components. One originates from a direct abstraction mechanism with product characteristics similar to those in the gas phase. The other is a trapping-desorption process yielding a thermal, Boltzmann-like distribution close to the surface temperature. This conclusion is consistent with that reached previously from independent measurements of OH product velocity distributions in complementary molecular-beam scattering experiments. It is further supported by the temporal profiles of OH/OD laser-induced fluorescence signals as a function of distance from the surface observed in the current experiments. The vibrational branching ratios for (v′=1)/(v′=0) for OH and OD have been found to be (0.07±0.02) and (0.30±0.10), respectively. The detection of vibrationally excited hydroxyl radicals suggests that secondary and/or tertiary hydrogen atoms may be accessible to the attacking oxygen atoms.
The authors describe the application of a combination of velocity map imaging and time-of-flight (TOF) techniques to obtain three-dimensional velocity distributions for surface photodesorption. They have established a systematic alignment procedure to achieve correct and reproducible experimental conditions. It includes four steps: (1) optimization of the velocity map imaging ion optics’ voltages to achieve optimum velocity map imaging conditions; (2) alignment of the surface normal with the symmetry axis (ion flight axis) of the ion optics; (3) determination of TOF distance between the surface and the ionizing laser beam; (4) alignment of the position of the ionizing laser beam with respect to the ion optics. They applied this set of alignment procedures and then measured Br(²P₃/₂) (Br) and Br(²P₁/₂) (Br∗) atoms photodesorbing from a single crystal of KBr after exposure to 193 nm light. They analyzed the velocity flux and energy flux distributions for motion normal to the surface. The Br∗ normal energy distribution shows two clearly resolved peaks at approximately 0.017 and 0.39 eV, respectively. The former is slightly faster than expected for thermal desorption at the surface temperature and the latter is hyperthermal. The Br normal energy distribution shows a single broad peak that is likely composed of two hyperthermal components. The capability that surface three-dimensional velocity map imaging provides for measuring state-specific velocity distributions in all three dimensions separately and simultaneously for the products of surface photodesorption or surface reactions holds great promise to contribute to our understanding of these processes.
Recent progress that has been made towards understanding the dynamics of collisions at the gas–liquid interface is summarized briefly. We describe in this context a promising new approach to the experimental study of gas–liquid interfacial reactions that we have introduced. This is based on laser-photolytic production of reactive gas-phase atoms above the liquid surface and laser-spectroscopic probing of the resulting nascent products. This technique is illustrated for reaction of O(³P) atoms at the surface of the long-chain liquid hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). Laser-induced fluorescence detection of the nascent OH has revealed mechanistically diagnostic correlations between its internal and translational energy distributions. Vibrationally excited OH molecules are able to escape the surface. At least two contributions to the product rotational distributions are identified, confirming and extending previous hypotheses of the participation of both direct and trapping-desorption mechanisms. We speculate briefly on future experimental and theoretical developments that might be necessary to address the many currently unanswered mechanistic questions for this, and other, classes of gas–liquid interfacial reaction.
Background: This basically anatomical study focuses on two items; firstly, the establishment of a system for the cartographic subdivision of the neopallium; secondly, the topographical correlation of extracranial landmarks and intracranial sites on the neopallium.
Materials and methods: The surface of the neopallium was subdivided into 15 sectors with reference to a newly introduced pattern of Primary Sulci. The topographical link between extracranial landmarks and certain intracranial sites (i.e. neopallium sectors) was elaborated by using a simple stereotactic device and a computer-assisted measurement device. Measurements were performed between points on the head's outer surface and on the isolated brain.
Results and Conclusions: The introduction of an anatomical three-dimensional coordinate system was an essential key issue for this investigation. This setting facilitated the measurements and calculations of the so-called indirect distances that were characterised by their alignment along the three orthogonal axes (x, y, z) of the anatomical coordinate system. The inter-individual comparison (16 adult horses [Equus caballus]) of the indirect distances revealed that each sector centre lay within a distinct morphometric residence area. The measured and calculated data also showed that each sector centre could be assigned to its proper extracranial landmark that - in comparison with other landmarks - was best suited for the optimal allocation of the sector centre point.
Molecular hydrogen production from amorphous solid water during low energy electron irradiation
(2017)
This work investigates the production of molecular hydrogen isotopologues (H2, HD, and D2) during low energy electron irradiation of layered and isotopically labelled thin films of amorphous solid water (ASW) in ultrahigh vacuum. Experimentally, the production of these molecules with both irradiation time and incident electron energy in the range 400 to 500 eV is reported as a function of the depth of a buried D2O layer in an H2O film. H2 is produced consistently in all measurements, reflecting the H2O component of the film, though it does exhibit a modest reduction in intensity at the time corresponding to product escape from the buried D2O layer. In contrast, HD and D2 production exhibit peaks at times corresponding to product escape from the buried D2O layer in the composite film. These features broaden the deeper the HD or D2 is formed due to diffusion. A simple random-walk model is presented that can qualitatively explain the appearance profile of these peaks as a function of the incident electron penetration.
Surface atomic relaxation and magnetism on hydrogen-adsorbed Fe(110) surfaces from first principles
(2016)
We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber–Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe–H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm−1, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.
The velocity distribution of He atoms evaporating from a slab of liquid dodecane has been simulated. The distribution composed of ∼10 000 He trajectories is shifted to fractionally faster velocities as compared to a Maxwell–Boltzmann distribution at the temperature of the liquid dodecane with an average translational energy of 1.05 × 2RT (or 1.08 × 2RT after correction for a cylindrical liquid jet), compared to the experimental work by Nathanson and co-workers (1.14 × 2RT) on liquid jets. Analysis of the trajectories allows us to infer mechanistic information about the modes of evaporation, and their contribution to the overall velocity distribution.
