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191.
We present an ab initio study of the optical absorption spectra of isolated as well as crystalline trans-polyacetylene. We include excitonic effects by solving the Bethe-Salpeter equation for the electron-hole two-particle correlation function. We observe that the strength of the electron-hole interactions drastically reduces when going from an isolated polymer chain to a crystalline arrangement. This is not only a result of enhanced screening in the 3D material, but also of the increased spatial extent of the exciton perpendicular to the polymer chains. We point out that these findings apply to crystalline phases of conjugated polymers and molecular crystals in general. 相似文献
192.
We report on ab-initio frozen-phonon calculations for the five A1g
Raman-active-modes of YBa2Cu3O7 atq=0. The determination of the equilibrium positions of the atoms Ba, Cu(2), O(2), O(3), O(4) as well as of phonon frequencies
and respective eigenvectors is based on the calculation of atomic forces within the LAPW-method. The general agreement between
our results and experimental structural data and phonon frequencies is good. Deviations are discussed in connection with the
local-density approximation. 相似文献
193.
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195.
A polymer-supported diketone was synthesized and used to fully protect/mask primary amines by the formation of a pyrrole ring. Various reactions can be performed on this system which then can be cleaved with full restoration of the amine functionality. The resin can also be recycled at least once without loss of purity of the final compound. [structure: see text] 相似文献
196.
We introduce an efficient lattice regularization scheme for quantum Monte Carlo calculations of realistic electronic systems. The kinetic term is discretized by a finite difference Laplacian with two mesh sizes, a and a', chosen so that the electrons can diffuse in a configuration space which is in practice indistinguishable from the continuum, and the different length scales in the system can be efficiently taken in account. The regularized Hamiltonian goes to the continuous limit for a --> 0 and allows the inclusion of nonlocal potentials in a consistent variational scheme, substantially improving the accuracy upon previous nonvariational approaches. 相似文献
197.
It is shown that the model of perfectly reflecting boundaries widely employed in cavity QED is unsuitable for systems that have long-wavelength excitations. A prime example is a free charged particle near a reflecting wall. Modeling the wall as perfectly reflecting from the outset ignores evanescent waves that couple to the particle through virtual excitations at low energies, which can lead to errors in order of magnitude and even sign. The example of a free electron near an imperfectly reflecting wall characterized by a constant frequency-independent refractive index n is investigated in detail by determining its energy shift relative to an electron in vacuum through both nonrelativistic and relativistic calculations. 相似文献
198.
199.
Mapping phosphorylation sites: a new strategy based on the use of isotopically labelled DTT and mass spectrometry 总被引:1,自引:0,他引:1
Amoresano A Marino G Cirulli C Quemeneur E 《European journal of mass spectrometry (Chichester, England)》2004,10(3):401-412
Phosphoproteomics, nowadays, represents a front line in functional proteomics as testified by the number of papers recently appearing in the literature. In an attempt to improve and simplify the methods so far suggested we have set up a simple isotope-coded approach to label and quantitate phospho-Ser/-Thr residues in protein mixtures. First of all, after appropriate oxidation of cysteine/cystine residues followed by tryptic hydrolysis, we have optimised and simplified the beta-elimination reaction to get the corresponding alkene moiety from the phosphate esters. This was achieved by (a) separating the elimination reaction from the addition reaction, (b) the use of Ba(OH)(2) as alkali reagent and (c) its further elimination by the simple addition of solid CO(2) to the peptide mixture. The Michael reaction was then performed, after the removal of BaCO(3) by centrifugation, by adding dithiothreitol (DTT) to the peptide mixture. Finally, the direct purification of the modified phosphopeptides was performed on a thiol-sepharose column. The availability of fully deuterated DTT, introducing a 6 Da difference with respect to the non-deuterated species, allows quantitation of the differential extent of signalling modification when analysed by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) and liquid chromatography/mass spectrometry. The entire procedure has been set up by using bovine alpha-casein, and resulted in the identification of all the phosphorylated tryptic peptides, including the tetraphosphorylated peptides, which escaped all previously reported procedures 相似文献
200.