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71.
72.
J.F. Owen T.T. Chen R.K. Chang B.L. Laube 《Journal of Electron Spectroscopy and Related Phenomena》1983,30(1):189
Surface enhanced Raman scattering of adsorbates on an Ag electrode in various electrolytes (e.g., 0.1–1.0 M KF, KCl, KBr, KI, K3PO4, and NaN3) has been investigated in an effort to elucidate the mechanism of the enhancement of water compared to that for other adsorbates. (It is well known, for example, that pyridine exhibits large enhancement in 0.1 M KCl while SERS from water is not detectable unless the salt concentration is raised to almost 1 M.) Use of an optical multichannel analyzer allowed rapid recording of Raman spectra, and SERS intensities of adsorbates could therefore be monitored simultaneously during a continuous oxidation-reduction cycle. Potential dependencies of SERS intensities when the electrode potential is cycled in a non-faradiac potential range immediately following oxidation and reduction indicate that adatoms are partially responsible for the Raman enhancement. Furthermore, the anions in the electrolyte play an important role in stabilizing these “active sites.” For this reason, the degree of enhancement is influenced by the solubility of the Ag compound formed during oxidation and the specific adsorption of the anions to the Ag surface. Preferential alignment of H2O molecules with their oxygen ends facing the surface at positive potentials, the tendency of anions in the electrolyte to disrupt hydrogen bonding with the water network, and the weak hydrogen bonding of H2O with the anions give rise to a SERS lineshape from adsorbed H2O molecules which is narrower than, and thus distinguishable from, the Raman line of bulk water. Thus, the degree to which the particular anions in the electrolyte disrupt hydrogen bonding among water molecules and reform hydrogen bonding between the anions and H2O molecules influences the SERS lineshape and the apparent enhancement of the H2 Raman emission. 相似文献
73.
Su-Yun Huang Chuhsing Kate Hsiao Ching-Wei Chang 《Annals of the Institute of Statistical Mathematics》2003,55(3):655-670
The article provides a refinement for the volume-corrected Laplace-Metropolis estimator of the marginal likelihood of DiCiccioet al. The correction volume of probability α in DiCiccioet al. is fixed and suggested to take the value α=0.05. In this article α is selected based on an asymptotic analysis to minimize
the mean square relative error (MSRE). This optimal choice of α is shown to be invariant under linear transformations. The
invariance property leads to easy implementation for multivariate problems. An implementation procedure is provided for practical
use. A simulation study and a real data example are presented. 相似文献
74.
We examine several interesting relationships and expressions involving Fourier-Feynman transform, convolution product and
first variation for functionals in the Fresnel class F(B) of an abstract Wiener space B. We also prove a translation theorem and Parseval's identity for the analytic Feynman integral.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
75.
For the minimal surfaces in Rn with Plateau boundary condition and establish the global existence and uniqueness of the flow as well as the continuous dependence of the initial datum. 相似文献
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本文提出应用小参数法 ,探讨 Markov链中相邻两次更新时刻内稀疏事件的概率估计问题 .建立了三种最重要的具有更新时间的概率模型 .通过小参数的引入和对概率式的幂展开 ,进而推证出幂渐近展开系数的模型估算法 .论证了无偏估计的重要定理 ,给出了概率估计式和无偏估计精度 .亦将许多算法扩展到Markov链的任意状态空间 相似文献
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