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131.
132.
Alkyl peroxy radicals are synthesized in a supersonic jet expansion by the initial production of alkyl radicals and subsequent reaction with molecular oxygen. Parent ions CH3OO+/CD3OO+ are observed employing vacuum ultraviolet (VUV) single photon ionizationtime-of-flight mass spectroscopy (TOFMS). Employing infrared (IR) + VUV photofragmentation detected spectroscopy, rotationally resolved infrared spectra of jet-cooled CH3OO and CD3OO radicals are recorded for the A 2A' <-- X 2A" transition by scanning the IR laser frequency while monitoring the CH3 + and CD3 + ion signals generated by the VUV laser. The band origins of the A 2A'<--X 2A" transition for CH3OO and CD3OO are identified at 7381 and 7371 cm(-1), respectively. Rotational simulation for the CH3OO and CD3OO 0(0) 0 transitions of A<--X yields a rotational temperature for these radicals of approximately 30 K. With the aid of ab initio calculations, two and five vibrational modes for the A 2A' excited electronic state are assigned for CH3OO and CD3OO radicals, respectively. Both experimental and theoretical results suggest that the ground electronic state of the ions of ethyl and propyl peroxy radicals are not stable although their ionization energies (IE) are less than 10.5 eV. The C2H5OO+/C3H7OO+ cations can readily decompose to C2H5 +/C3H7 + and O2. This is partially responsible for the inability of IR+VUV photofragmentation spectroscopy to detect the near IR A<--X electronic transition for these radicals. 相似文献
133.
Neutral niobium and tantalum clusters (Nbn and Tan) are generated by laser ablation and supersonic expansion into a vacuum and are reacted in a pickup cell with various low pressure (approximately 1 mTorr) unsaturated hydrocarbons (acetylene, ethylene, propylene, 1-butene, 1,3-butadiene, benzene, and toluene) under nearly single collision conditions. The bare metal clusters and their reaction products are ionized by a 193 nm laser and detected by a time of flight mass spectrometer. Partially and fully dehydrogenated products are observed for small (nor=m) neutral metal clusters, respectively, with m ranging from 2 to 5 depending on the particular hydrocarbon. In addition to primary, single collision products, sequential addition products that are usually fully dehydrogenated are also observed. With toluene used as the reactant gas, carbon loss products are observed, among which Nb8C12 and Ta8C12 are particularly abundant, indicating that the Met-Car molecule M8C12 can be formed from the neutral metal cluster upon two collisions with toluene molecules. The dehydrogenation results for low pressure reactions are compared with those available from previous studies employing flow tube (high pressure) reactors. Low pressure and high pressure cluster ion reactions are also compared with the present neutral metal cluster reactions. Reactions of unsaturated hydrocarbons and metal surfaces are discussed in terms of the present neutral cluster results. 相似文献
134.
The search for a co-crystal of benzidine as a bifunctional hydrogen-bond donor with potential hydrogen-bond acceptors has instead revealed four polymorphs of the source material benzidine for which, somewhat surprisingly, no structure has been reported as of the November 2005 update of the CSD. All four structures are characterized by a rather unusual number of molecules in the asymmetric unit (Z' = 1.5, 3, and 4.5), which are found in only 0.25%, 0.4%, and 0.002% of structures in the CSD. Forms I and IV (Z' = 4.5) exhibit very similar crystal habits and are not distinguishable visually. In all forms except Form II (Z' = 3), one of the molecules lies on a crystallographic inversion center, requiring the molecule to be planar; other molecules are nonplanar. Spectroscopic and thermodynamic characterizations of the system, including at least two possible additional forms of benzidine obtained by HT polymorph screening are reported. 相似文献
135.
Pure neutral (CO2)n clusters and mixed (CO2)n(H2O)m clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV. The distribution of pure (CO2)n clusters decreases roughly exponentially with increasing cluster size. During the ionization process, neutral clusters suffer little fragmentation because almost all excess cluster energy above the vertical ionization energy is taken away by the photoelectron and only a small part of the photon energy is deposited into the (CO2)n cluster. Metastable dissociation rate constants of (CO2)n+ are measured in the range of (0.2-1.5) x 10(4) s(-1) for cluster sizes of 5< or =n< or =16. Mixed CO2-H2O clusters are studied under different generation conditions (5% and 20% CO2 partial pressures and high and low expansion pressures). At high CO2 concentration, predominant signals in the mass spectrum are the (CO2)n+ cluster ions. The unprotonated cluster ion series (CO2)nH2O+ and (CO2)n(H2O)2+ are also observed under these conditions. At low CO2 concentration, protonated cluster ions (H2O)nH+ are the dominant signals, and the protonated CO2(H2O)nH+ and unprotonated (H2O)n+ and (CO2)(H2O)n+ cluster ion series are also observed. The mechanisms and dynamics of the formation of these neutral and ionic clusters are discussed. 相似文献
136.
Three experiments tested the hypothesis that fundamental frequency (fo) discrimination depends on the resolvability of harmonics within a tone complex. Fundamental frequency difference limens (fo DLs) were measured for random-phase harmonic complexes with eight fo's between 75 and 400 Hz, bandpass filtered between 1.5 and 3.5 kHz, and presented at 12.5-dB/component average sensation level in threshold equalizing noise with levels of 10, 40, and 65 dB SPL per equivalent rectangular auditory filter bandwidth. With increasing level, the transition from large (poor) to small (good) fo DLs shifted to a higher fo. This shift corresponded to a decrease in harmonic resolvability, as estimated in the same listeners with excitation patterns derived from measures of auditory filter shape and with a more direct measure that involved hearing out individual harmonics. The results are consistent with the idea that resolved harmonics are necessary for good fo discrimination. Additionally, fo DLs for high fo's increased with stimulus level in the same way as pure-tone frequency DLs, suggesting that for this frequency range, the frequencies of harmonics are more poorly encoded at higher levels, even when harmonics are well resolved. 相似文献
137.
Bourgeois P Sato Y Shaw J Alarcon R Bernstein AM Bertozzi W Botto T Calarco J Casagrande F Distler MO Dow K Farkondeh M Georgakopoulos S Gilad S Hicks R Holtrop M Hotta A Jiang X Karabarbounis A Kirkpatrick J Kowalski S Milner R Miskimen R Nakagawa I Papanicolas CN Sarty AJ Sirca S Six E Sparveris NF Stave S Stiliaris E Tamae T Tsentalovich G Tschalaer C Turchinetz W Zhou ZL Zwart T 《Physical review letters》2006,97(21):212001
The mean square polarizability radii of the proton have been measured for the first time in a virtual-Compton-scattering experiment performed at the MIT-Bates out-of-plane scattering facility. Response functions and polarizabilities obtained from a dispersion analysis of the data at Q2 = 0.057 GeV2/c2 are in agreement with O(p3) heavy baryon chiral perturbation theory. The data support the dominance of mesonic effects in the polarizabilities. 相似文献
138.
The feasibility of a k-space trajectory that samples data on a set of 3D shells is demonstrated with phantom and volunteer experiments. Details of an interleaved multi-shot, helical spiral pulse sequence and a gridding reconstruction algorithm that uses Voronoi diagrams are provided. The motion-correction properties of the shells k-space trajectory are described. It is shown that when used in conjunction with three point markers, k-space data acquired with the shells trajectory provide a generalization of the RINGLET method, allowing for correction of arbitrary rigid-body motion with six degrees of freedom. Use of dedicated navigator echoes or redundant acquisitions of k-space data are not required. Retrospective motion correction is demonstrated with controlled phantom experiments and with seven healthy human volunteers. The motion correction is shown to improve the images, both qualitatively and quantitatively with a metric calculated from image entropy. Advantages and challenges of the shells trajectory are discussed, with particular attention to acquisition efficiency. 相似文献
139.
The paper at hand is concerned with creating a flexible wavelet theory on the three sphere S3 and the rotation group SO(3). The theory of zonal functions and reproducing kernels will be used to develop conditions for an admissible wavelet. After explaining some preliminaries on group actions and some basics on approximation theory, we will prove reconstruction formulas of linear and bilinear wavelet transformed L2‐functions on S3. Moreover, specific examples will be constructed and visualized. Second, we deal with the construction of wavelets on the rotation group SO(3). It will be shown that the Radon transform of a wavelet packet on SO(3) gives a wavelet packet on S2 for every fixed detection direction. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
140.
This paper examines the self-assembly of cyclic β-tripeptides using density functional theory. On the basis of literature precedents, these cyclic peptides were expected to self-assemble into cylindrical structures by stacking through backbone-backbone hydrogen bonding. Our calculations show that such stacking is energetically favorable, that the association energy per cyclic peptide decreases (becomes more favorable), and that the overall macrodipole moment of the cylindrical assembly increases with the number of stacked rings, for up to eight rings. For a structure in which two peptide ring units are joined through a single side chain-side chain covalent linker, the association energy between the two rings is favorable, albeit less so than for the unlinked rings. Significantly, the association energy in the dimers is only weakly dependent on the length (above a certain minimum) and conformation of the covalent linkers. Finally, as a plausible route for controlling assembly/disassembly of nanocylinders, we show that, for a pair of rings, each bearing a single amino-functionalized side chain, protonation of the amino group results in a strongly positive (unfavorable) association energy between the two rings. 相似文献