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31.
The structures, energies, and natural atomic charges of 2-dimethylaminophenol oxide, 2-Me2N-(O)C6H4OH, and 2-dimethylphosphinylphenol, 2-Me2P(O)C6H4OH, in three different conformations were computed at the ab initio MP2/6-31G* level. Computed natural charges indicate distributions of electron density in amine oxides and phosphine oxides that are quite different from what is normally assumed on the basis of the formal charges in the usual representations of these compounds. The charges on nitrogen and phosphorus in these compounds are typically computed to be approximately zero on nitrogen and +2 on phosphorus, and the oxygen is considerably more negative in the phosphine oxide than in the amino oxide. Electronegativity differences thus play a larger role and formal charges a smaller one in determining atomic charges in these compounds than is generally believed. Despite the more negative oxygen in phosphine oxides, amine oxides are computed to be considerably more basic when participating in hydrogen bonding. Calculations treating the computed natural charges on these six conformations as point charges for classical approximations of the coulombic energies support the idea that the quantum mechanically computed relative energies are largely determined by coulombic interactions. 相似文献
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M. B. Freiler M. C. Shih S. Kim M. Levy I. P. Herman R. Scarmozzino R. M. Osgood Jr. 《Applied Physics A: Materials Science & Processing》1996,63(2):143-151
We present a study of pattern-transfer and etch-induced damage in photon-induced cryoetching. Features with effective radii as small as 100 nm have been formed in both bulk and layered GaAs/AlGaAs materials. A measurement of the photoluminescence of etch-defined deep- submicrometer structures material suggests that this form of etching results in minimal process-induced damage. Modeling of the luminescence vs feature size for these features shows that the luminescence is limited only by carrier diffusion and non-radiative surface recombination. 相似文献
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A. B. Levy 《Set-Valued Analysis》1993,1(4):379-392
Epi-derivatives have many applications in optimization as approached through nonsmooth analysis. In particular, second-order epi-derivatives can be used to obtain optimality conditions and carry out sensitivity analysis. Therefore the existence of second-order epi-derivatives for various classes of functions is a topic of considerable interest. A broad class of composite functions on
n
called fully amenable functions (which include general penalty functions composed withC
2 mappings, possibly under a constraint qualification) are now known to be twice epi-differentiable. Integral functionals appear widely in problems in infinite-dimensional optimization, yet to date, only integral functionals defined by convex integrands have been shown to be twice epi-differentiable, provided that the integrands are twice epi-differentiable. Here it is shown that integral functionals are twice epi-differentiable even without convexity, provided only that their defining integrands are twice epi-differentiable and satisfy a uniform lower boundedness condition. In particular, integral functionals defined by fully amenable integrands are twice epi-differentiable under mild conditions on the behavior of the integrands.This work was supported in part by the National Science Foundation under grant DMS-9200303. 相似文献
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A new chiral binaphthyl salen ligand with rigid polyaromatic sidearms gives monohelical complexes (Fe(II) and Zn(II)) of predetermined handedness. 相似文献
40.
I. A. Bashmakov V. A. Dorosinets V. K. Ksenevich A. A. Mel’nikov F. N. Kaputskii 《Russian Journal of Applied Chemistry》2007,80(2):285-289
A new procedure was developed for preparing carbon films with magnetic metal nanoparticles by thermolysis of a polymer precursor. The conditions for preparing carbon films with required surface concentration of the metal nanoparticles and hence with dielectric or metallic properties were determined. 相似文献