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1.
2.
Muon irradiation of pure liquid 3‐chloropropene, CH2=CH-CH2Cl, yields a primary radical, \dot\mboxCH2-CHMu-CH2Cl, and a secondary radical, MuCH2-\rm\dot\mboxCH-CH2Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH2-\rm\dot\mboxC(CH3)-CH2Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs)
have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature
variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta
axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis
of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like
groups, -CH3,-CH2Cl and -CH2Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information
on the effects of Mu substitution for H.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
3.
Ghandi K Addison-Jones B Brodovitch JC McCollum BM McKenzie I Percival PW 《Journal of the American Chemical Society》2003,125(32):9594-9595
Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied. 相似文献
4.
A computational study has been performed to examine the reactions of a model beta-diketiminatoaluminium (I) complex with the hydrogen atom and with the electron. It was found that the hydrogen atom adds to the metal centre exothermically (DeltaH(rxn)=-202 kJ mol(-1)), and the spin density in the resulting radical resides entirely on the beta-diketiminato ligand. The spin density of the corresponding radical anion is very similar to the H-adduct. 相似文献
5.
6.
Feng Ji Paul W. Percival Jean-Claude Brodovitch Brenda Addison-Jones Stanislaw Wlodek 《Hyperfine Interactions》1994,87(1):853-858
Muonium adds to allyl chloride, CH2=CHCH2Cl, to form two radicals: MuCH2CHCH2Cl (main product) and CH2CHMuCH2Cl (minor product). Both radicals were fully characterized bySR andLCR. In the main product, the LCR lines due to the35Cl and37Cl nuclei were observed. Also, the temperature dependence of various hyperfine coupling constants (hfc) indicates that both Mu and Cl eclipse the unpaired electronp
2-orbital in the minimum energy conformation. For the fragment-CH2Cl, the presence of Mu in the-position is found to affect significantly the hfc of Cl in the-position; an internal rotational barrier of 12 kJ mol–1 was estimated using a simpleV
2 torsional potential. 相似文献
7.
Martina Schwager Emil Roduner Ivan D. Reid Paul W. Percival Jean-Claude Brodovitch Stanislaw Wlodek Robert F. Marzke 《Hyperfine Interactions》1994,87(1):859-864
SR spectra of the ethyl radical adsorbed on porous silica were observed in transverse and in longitudinal magnetic fields in the temperature range 190–298 K. The line widths reflect the dynamic partial averaging of the hyperfine anisotropy due to reorientation and surface diffusion. 相似文献
8.
9.
Dimitrios Pavlidis Jefferson L. M. A. Gomes Zhihua Xie James R. Percival Christopher C. Pain Omar K. Matar 《国际流体数值方法杂志》2016,80(4):256-282
This paper develops methods for interface‐capturing in multiphase flows. The main novelties of these methods are as follows: (a) multi‐component modelling that embeds interface structures into the continuity equation; (b) a new family of triangle/tetrahedron finite elements, in particular, the P1DG‐P2(linear discontinuous between elements velocity and quadratic continuous pressure); (c) an interface‐capturing scheme based on compressive control volume advection methods and high‐order finite element interpolation methods; (d) a time stepping method that allows use of relatively large time step sizes; and (e) application of anisotropic mesh adaptivity to focus the numerical resolution around the interfaces and other areas of important dynamics. This modelling approach is applied to a series of pure advection problems with interfaces as well as to the simulation of the standard computational fluid dynamics benchmark test cases of a collapsing water column under gravitational forces (in two and three dimensions) and sloshing water in a tank. Two more test cases are undertaken in order to demonstrate the many‐material and compressibility modelling capabilities of the approach. Numerical simulations are performed on coarse unstructured meshes to demonstrate the potential of the methods described here to capture complex dynamics in multiphase flows. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
10.
Farhangi MM Graham PJ Choudhury NR Dolatabadi A 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1290-1303
Coalescence of a falling droplet with a stationary sessile droplet on a superhydrophobic surface is investigated by a combined experimental and numerical study. In the experiments, the droplet diameter, the impact velocity, and the distance between the impacting droplets were controlled. The evolution of surface shape during the coalescence of two droplets on the superhydrophobic surface is captured using high speed imaging and compared with numerical results. A two-phase volume of fluid (VOF) method is used to determine the dynamics of droplet coalescence, shape evaluation, and contact line movement. The spread length of two coalesced droplets along their original center is also predicted by the model and compared well with the experimental results. The effect of different parameters such as impact velocity, center to center distance, and droplet size on contact time and restitution coefficient are studied and compared to the experimental results. Finally, the wetting and the self-cleaning properties of superhydrophobic surfaces have been investigated. It has been found that impinging water drops with very small amount of kinetic impact energy were able to thoroughly clean these surfaces. 相似文献