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991.
Björn Rahn Dr. Rui Wen Lukas Deuchler Johannes Stremme Dr. Andreas Franke Prof. Dr. Eckhard Pehlke Prof. Dr. Olaf M. Magnussen 《Angewandte Chemie (International ed. in English)》2018,57(21):6065-6068
Coadsorbed anions are well‐known to influence surface reactivity and dynamics at solid–liquid interfaces. Here we demonstrate that the chemical nature of these spectator species can entirely determine the microscopic dynamic behavior. Quantitative in situ video‐STM data on the surface diffusion of adsorbed sulfur atoms on Cu(100) electrodes in aqueous solution covered by bromide and chloride spectators, respectively, reveal in both cases a strong exponential potential dependence, but with opposite sign. This reversal is highly surprising in view of the isostructural adsorbate arrangement in the two systems. Detailed DFT studies suggest an anion‐induced difference in the sulfur diffusion mechanism, specifically an exchange diffusion on the Br‐covered surface. Experimental evidence for the latter is provided by the observation of Cu vacancy formation in the Br system, which can be rationalized by a side reaction of the sulfur exchange diffusion. 相似文献
992.
993.
Olaf Steinbach 《PAMM》2003,3(1):539-542
A hierarchical multilevel preconditioner is constructed for an efficient solution of a first kind boundary integral equation with the single layer potential operator discretized by a boundary element method. This technique is based on a hierarchical clustering of all boundary elements as used in fast boundary element methods. This hierarchy is applied to define a sequence of nested boundary element spaces of piecewise constant basis functions as used in the definition of the preconditioning multilevel operator. 相似文献
994.
Joachim Heinicke Nidhi Gupta Shreeyukta Singh Anushka Surana Olaf Kühl Raj K. Bansal Konstantin Karaghiosoff Martin Vogt 《无机化学与普通化学杂志》2002,628(13):2869-2876
1H‐1, 3‐Benzazaphospholes react with M(CO)5(THF) (M = Cr, Mo, W) to give thermally and relatively air stable η1‐(1H‐1, 3‐Benzazaphosphole‐P)M(CO)5 complexes. The 1H‐ and 13C‐NMR‐data are in accordance with the preservation of the phosphaaromatic π‐system of the ligand. The strong upfield 31P coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield‐shifts of phosphine‐M(CO)5 complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH‐function. The resulting ambident 1, 3‐benzazaphospholide anions prefer a μ2‐coordination of the η5‐CpNi‐fragment at phosphorus to coordination at nitrogen or a η3‐heteroallyl‐η5‐CpNi‐semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a η5‐CpNi‐benzazaphospholide. The latter is a P‐bridging dimer with a planar Ni2P2 ring and trans‐configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four‐membered ring. 相似文献
995.
Olaf Hansen 《PAMM》2003,2(1):414-415
The radiosity equation is an integral equation of the second kind which describes the energy exchange by radiation between surfaces in R3. It is assumed that all surfaces are Lambertian reflectors and that all emitters are diffusive emitters. The radiosity equation plays an important role for the calculation of photo realistic images with the help of computers. Many surfaces which are used in practical calculations are only piecewise smooth and contain edges or corners. In this contribution we present regularity results for the solution of the radiosity equation in the vicinity of corners. The space of piecewise continuous functions is not suitable for this equation and we construct a new function space which contains the solution of the radiosity equation. 相似文献
996.
997.
Carsten Puke Kai Schmengler Kristin Kirschbaum Olaf Conrad Dean M. Giolando 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(12):e542-e542
In the title compound, tetrakis(tetrahydrofuran)lithium(I) tri‐μ‐phenylthiolato‐bis[tris(phenylthiolato)titanate(IV)], [Li(C4H8O)4][Ti2(C6H5S)9], (I), the central structural motif of the [Ti2(SC6H5)9]? anion features a face‐sharing bi‐octahedron. The charge is balanced with a [Li(C4H8O)4]+ cation. The asymmetric unit contains Ti, Li and a heavily disordered tetrahydrofuran molecule on a threefold axis, and two terminal and a bridging thiophenolate moiety and a slightly disordered tetrahydrofuran molecule on general positions. 相似文献
998.
We investigate the dynamics of cracking of a brittle coating covering an elastically stretched substrate. We consider here a scalar model (an electrical analogue) in order to describe fractures in thin and in thick films. The model captures the essential features of the fragmentation of coatings and allows us to classify different temporal regimes in the cracking process and to obtain several basic patterns of the cracks' morphology. 相似文献
999.
The nanoscale interface between two immiscible electrolyte solutions (nanoITIES) is an emerging versatile analytical platform. Analytical advantages of chemical analysis using the nanoITIES include imaging with nanometer spatial resolution, probing fast dynamics with millisecond temporal resolution and fast response times, selectively detecting analytes, probing fundamental chemical processes (e.g., diffusion profiles), and versatile sensing of metal ions, proteins, neurotransmitters, ionic and neutral species, redox-active and non-redox active analytes, etc. We present here a brief theoretical background of the nanoITIES and experimental advances from the past five years. These advances include imaging of nanopores, probing diffusion profiles, biosensing, a new pH modulation mechanism for sensing neutral species, and studying exocytosis from Aplysia californica neurons. 相似文献
1000.
H. Lars Deubner Stefan S. Rudel Malte Sachs Clemens Pietzonka Prof. Dr. Antti J. Karttunen Dr. Sergei I. Ivlev Matthias Müller Dr. Matthias Conrad Prof. Dr. Ulrich Müller Prof. Dr. Florian Kraus 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(25):6402-6411
The redetermination of the crystal structure of trigonal UCl6, which is the eponym for the UCl6 structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl6 molecule (2.41 and 2.51 Å). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) Å). This room temperature modification, called rt-UCl6, crystallizes in the trigonal space group P m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) Å, V=616.9(2) Å3, Z=3 at T=253 K. A new low-temperature (lt) modification of UCl6 is also presented that was obtained by cooling a single crystal of rt-UCl6. The phase change occurs between 150 and 175 K. lt-UCl6 crystallizes isotypic to a low-temperature modification of SF6 in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) Å, β=96.68(2)°, V=1203.6(5) Å3, Z=6 at 100 K. The Cl anions form a close-packed structure corresponding to the α-Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr5 a new modification was obtained that crystallizes in the triclinic crystal system, space group P , No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) Å, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) Å3, Z=3 at T=100 K. In this structure the UBr5 units are dimerized to U2Br10 molecules. The Br anions also form a close-packed structure of the α-Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX5 (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α-PaBr5 is probably not correct. 相似文献