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51.
52.
David Loffreda 《Surface science》2006,600(10):2103-2112
Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries. 相似文献
53.
All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties. 相似文献
54.
We have performed total-energy calculations to study theoretical scanning tunneling microscopy (STM) images of the Si(1 1 1)3 × 2 surfaces induced by the adsorption of alkaline-earth metals (AEMs). Previously, in a series of works on Ba/Si(1 1 1) system, we have found that the observed Si(1 1 1)3 × 1-Ba LEED phase indeed has a 3 × 2 periodicity with a Ba coverage of 1/6 ML and the HCC substrate structure. Based on results of the Ba case, we proposed that the HCC structure is also adopted for other AEM atoms, which was confirmed by our recent work. In this paper, we mainly report the STM simulations for different AEM systems to compare with existing experimental data. We discuss the difference in the detailed STM images for different AEM adsorbates. Especially, the difference in filled-state images between Mg and other AEM atoms is attributed to the strong Mg-Si interaction. 相似文献
55.
Materials from the Mn(0.5−x)CaxTi2(PO4)3 (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, 31P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R
space group. Mn2+/Ca2+ ions occupy only the M1 sites in the Ti2(PO4)3 framework. The divalent cations are ordered in one of two M1 sites, except for the Mn0.50Ti2(PO4)3 phase, where a small departure from the ideal order is observed by XRD and 31P MAS NMR. The electrochemical behaviour of Mn0.50Ti2(PO4)3 and Mn(0.5−x)CaxTi2(PO4)3 phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti2(PO4)3 framework. In the 0≤y≤2 range, the OCV curves of Li//LiyMn0.50Ti2(PO4)3 cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li(1+y)Ti2(PO4)3 and Li//LiyMn0.50Ti2(PO4)3 shows that the intercalation occurs first in the unoccupied M1 site of Mn0.50Ti2(PO4)3 at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn0.50Ti2(PO4)3 on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn0.50Ti2(PO4)3, the stability of Mn2+ either in an octahedral or tetrahedral environment facilitates cationic migration. 相似文献
56.
Gianluigi Luppi Rodrigo J. Corrêa Angelo C. Pinto Quirinus B. Broxterman Claudia Tomasini 《Tetrahedron》2006,62(51):12017-12024
The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic. 相似文献
57.
58.
基于Prony算法的Delsuc谱预测是目前NMR LPSVD(Linear Prediction SingularValue Decomposition)法中比较实用的方法。但在高噪声的条件下,时有失峰和假峰出现且要事先知道谱的峰数。本文通过跟踪迭代过程发现Delsuc法的判别因子r_(mis) 很难选定。如果它太小会失峰,而过大又会出现假峰。同时,由于噪声的影响,弱信号的采样点之间的相关性比强信号小,从而在迭代过程中会增加数值不稳定性。文中引入峰面积判据来改善Delsuc法,经模拟与实验均证明结果有效。 相似文献
59.
Ryuhei Wakita Masanori Miyakoshi Yohji Nakatsuji Mitsuo Okahara 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):127-139
A series of noncyclic neutral ionophores has been synthesized by the reaction of oligoethylene glycol dihalides with 8-quinolinol. Complexation properties for alkali metal picrates were evaluated from solvent extraction and bulk liquid membrane transport experiments. Complexation profiles of the newly synthesized ionophores with a hexyl chain were similar to those of their homologues without the hexyl chain in the extraction experiments. Among them, the pentaethylene glycol derivatives showed the highest extraction efficiency and selectivity towards potassium ion. From the1H NMR spectra (400 MHz), the change in chemical shifts of the aromatic protons upon the addition of alkali metal thiocyanates suggested the existence of a stabilization effect which is caused by intramolecular stacking conformations between the quinoline rings during complexation. Aryl stacking interactions depend on the size of the cations and on the chain length of the oligoethylene glycol. The relationship between transport ability towards alkali metal cations and lipophilicity of these ionophores is also discussed. 相似文献
60.