The adsorption of atomic S on the Fe(1 1 0) surface is examined using density functional theory (DFT). Three different adsorption sites are considered, including the atop, hollow and bridge sites and the S is adsorbed at a quarter monolayer coverage in a p(2 × 2) arrangement. The hollow site is found to be the most stable, followed by the bridge and atop sites. At all three sites, S adsorption results in relatively minor surface reconstruction, with the most significant being that for the hollow site, with lateral displacements of 0.09 Å. Comparisons between S-adsorbed and pure Fe surfaces revealed reductions in the magnetic moments of surface-layer Fe atoms in the vicinity of the S. At the hollow site, the presence of S causes an increase in the surface Fe d-orbital density of states between 4 and 5 eV. However, S adsorption has no significant effect on the structure and magnetic properties of the lower substrate layers. 相似文献
The exponential X-ray transform arises in single photon emission computed tomography and is defined on functions on ?n by , where μ is a constant. Approximate inversion, and inversion formulae of filtered back-projection type are derived for this operator in all dimensions. In particular, explicit formulae are given for convolution kernels (filters) K corresponding to a general point spread function E that can be used to invert the exponential X-ray transform via a filtered back-projection algorithm. The results extend and refine work of Tretiak and Metz17. 相似文献
Experimental conditions have now been developed whereby o-bromophenyllithium(II) may be prepared in excellent yields and used as an organometallic intermediate for the synthesis of a variety of ortho bromo substituted phenyl compounds (o-BrC6H4X). THe thermal stability, decomposition products and reactions of II wre studied. REactions between II and a variety of substrates, e.g., CO2, dimethylformamide, fluorinated esters, hexafluorobenzene, and organosilicon chlorides were examined. 相似文献
Khusimone (1), one of the main odor-donating compounds of vetiver oil is subject of the following study on structure/odor relationship. The omittance of the ethano bridge of the tricyclic khusimone leads to a bicyclic system. The stereoselective approach to this degraded structure is described, and the olfactory properties are studied. The key step of the synthesis of the hydrindane nucleus is based on a highly diastereoselective conjugate addition to a chiral oxo-cyclopentene-2-carboxylate. 相似文献
A method for the treatment of long-dimensional chemical data arrays is presented in this work with the aim of maximising classification models. The method is based on the construction of fingerprints and the subsequent generation of a similarity matrix. The similarity calculation has been modified through a scaling process to take into account different significance shown by the variables. The method was applied to spectral measurements of wines and several aspects were studied, namely: threshold considered in the construction of fingerprints and patterns, weighting factor used for scaling, normalisation method, etc. The application of both Principal Components Analysis and Soft-Independent Modelling of Class Analogies to the similarity matrices gave better classifications of the information than those obtained using original data. 相似文献
In this paper, we propose a new method for clustering of chemical databases based on the representation of measurements of structural similarity onto multidimensional spaces. The proposed method permits the tuning of the clustering process through the selection of the dimension of the projection space, the normal vectors and the sensibility of the projection process. The structural similarity of each element regarding to the database elements is projected onto the defined spaces generating clusters that represent the characteristics and diversity of the database and whose size and characteristics can be easily adjusted. 相似文献
All-electron ab initio Hartree–Fock (HF ), valence configuration interaction (CI ), and multiconfiguration self-consistent-field (CASSCF ) calculations have been applied to investigate the electronic states of the CrC molecule. The molecule is predicted as having four low-lying electronic states, 3∑?, 5∑?, 7∑?, and 9∑?, separated by an energy gap of 0.55 eV from the next higher-lying state, 1∑?, which is followed by the states 5Π and 7Π. The four lowest-lying electronic states are due to the coupling of the angular momenta of the 6Sg Cr+ ion with those of the 4Su C? anion. The chemical bond in the 3∑? ground state can be viewed as a quadruple bond composed of two σ and two π bonds. One σ bond is due to the formation of a molecular orbital that is doubly occupied. The remaining bonds, i.e., one σ and two π bonds, arise from valence-bond couplings. The π bonds originate from the valence-bond couplings of the electrons in the C 2pπ orbitals with those in the Cr 3dπ orbitals. The σ bond originates from the valence-bond coupling of the C 2pσ electron with an electron in the Cr 4s, 4p hybrid that is polarized away from the C atom. 相似文献
The molecular dynamics method has been applied to investigate the conformations of n-butyl ligands immobilised onto an amorphous silica surface analogous to those utilised with silica-based RP-HPLC sorbents. Three systems were constructed which corresponded to ligand densities of 1.64, 2.67 and 3.69 μmol/m2. A number of parameters related to the structure of the sorbent materials were derived in order to characterise the molecular properties of each system. These parameters included the hydrocarbon layer thickness, the frequency of gauche conformations, the distance distribution for carbon atoms and the diffusion coefficients of individual atoms in the n-butyl ligands. From these properties, the positions of chains with respect to the surface as well as their mobility were estimated. It was found that at higher densities, the n-butyl chains are predominantly perpendicular to the surface while at low density they are highly tilted or lying almost parallel to the surface. The degree of ligand flexibility decreased with increasing surface density. Mobility of individual carbon atoms as well as chain disorder increased with distance from the surface for all ligand densities. The simulated properties of n-butyl chains immobilised to a silica surface correlated well with results obtained by Fourier transform IR and 13C-cross polarisation magic angle spinning NMR experimental methods and statistical predictions of the behaviour of immobilised chains. 相似文献
In order to understand the patterns of the adsorption equilibrium of Cr (III) on activated carbon, the adsorption process
was studied by two different ways: classical batch experiments on commercial Norit and Merck activated carbons and their oxidized
forms in a wide range of pHs; and extended time-based tests at the same pH values on the same adsorbents. This approach allowed
us to understand the role of texture, chemical carbon surface functionality and experimental conditions (initial pH of the
solution, contact time and adsorbate/adsorbent ratio) on the effectiveness of Cr (III) removal. The adsorption process of
Cr (III) at (24 ± 1∘C) on Merck and Norit activated carbons and their oxidized forms were studied at pH values between 1.5 and 5 (either adjusted
or buffered). Chromium concentration was fixed at 200 ppm. The carbon loading ranged from 1.2 to 20 g/l. The carbon/Cr (III)
solution contact time was varied from 0.5–1 month to 5 months, to ensure that the saturation of the carbon level was reached.
According to the data obtained, the presence of carboxylic groups on carbon surface seems to enhance Cr (III) uptake at initial
pH of the solution in the range between 2 and 4. Depending on the nature of the adsorbent surface chemistry, the contact time
to reach equilibrium may range from 3 to 5 months. There is an optimum carbon loading which limits the Cr (III) uptake/removal
at given pH value. In order to understand the adsorption process, an ion exchange, surface complex and surface precipitation
were considered.
This paper was presented in the 5th Brazilian Meeting on Adsorption, held at Natal, Brazil, 18-21 July, 2004. 相似文献