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71.
Standard Gibbs free energies, enthalpies, and entropies for the dissociation of various aliphatic carboxylic acids are obtained through potnetiometric and calorimetric measurements in water-tert-butyl alcohol mixtures. Results are discussed in terms of solvent structural effects for the proton exchange reaction and in terms of the compensation law to explain enthalpic and entropic effects.Part I, ref 4; Part II,Thermochimica Acta
6, 283 (1973). 相似文献
72.
Majda Sekkal Jean-Pierre Huvenne Pierre Legrand Bernard Sombret Jean-Claude Mollet Anne Mouradi-Givernaud Marie-Claire Verdus 《Mikrochimica acta》1993,112(1-4):1-10
Unlike carrageenans, agars have not been studied very extensively by infrared spectroscopy, in so far as the structures of this kind of polygalactanes are not as well defined as carrageenans. However, in a previous work we have carried out a vibrational analysis of both carrageenans and agars and some important assignments of the main absorptions have been made. Consequently, the present work has been undertaken in order to identify agars without any extraction directly in various seaweeds using the infrared microspectrometry method. The main advantage of this method is that the sample consists only of a dehydrated algal section. The red algaeGradlaria verrucosa has been the subject of the present study. In the first place, spectra of extracted agars were recorded, as they can help us to confirm the nature of the compound identified by this technique. In a second stage, spectra of different parts of the sections have been carried out. The comparison between the resulting spectra with those of the extracted polysaccharides, has demonstrated, firstly that the best results are obtained from the cortical area, because, as expected, the agar is mainly located in the cell wall of this area of the algae. Indeed, the feature bands of agars are all observed, especially the intense ones between 1000 and 1100 cm–1 and the more characteristic absorptions in the wavenumbers range below 1000 cm–1 so as the ones at 988, 965, 930, 890, 870, 771 and 741 cm–1. Secondly, it may be also identified in smaller amounts in the medullar area, the cells are greater than in the cortical area and the cytoplasm is preponderent. However, in the latter case a coexisting polysaccharide, present in a considerable quantity and called floridean starch (Its structure is not very well known, as it varies from one algae to another), masks the spectra of agar, as its spectrum is very similar to those of polygalactanes. 相似文献
73.
The 1H and 13C NMR resonances of 15 N,N'-diacylproflavines were assigned completely and unequivocally using a concerted application of one- and two-dimensional experiments (DEPT, gs-COSY, gs-HMQC and gs-HMBC). 相似文献
74.
The valence one-electron and shake-up ionization spectra of stella-2,6-diene, stella-2,6-dione, bicyclo-[2.2.2]-octane-2,5-dione, and bicyclo-[2.2.1]-heptane-2,5-dione have been exhaustively studied, up to the double ionization threshold and beyond, by means of one-particle Green's function theory. This study is based on calculations employing the outer-valence Green's function and the third-order algebraic diagrammatic construction schemes, along with a variety of basis sets. A comparison is made with available ultraviolet (He I) photoelectron and (e, 2e) electron-impact ionization spectra, with main focus on the identification of spectral fingerprints for cyclic strains and through-bond pi-conjugation. As a byproduct, our results demonstrate that it is impossible to reliably assign complex (e, 2e) ionization spectra by resorting only to Hartree-Fock or Kohn-Sham orbital energies and to the related electron momentum distributions. 相似文献
75.
Cinchetti M Sánchez Albaneda M Hoffmann D Roth T Wüstenberg JP Krauss M Andreyev O Schneider HC Bauer M Aeschlimann M 《Physical review letters》2006,97(17):177201
The femtosecond magnetization dynamics of a thin cobalt film excited with ultrashort laser pulses has been studied using two complementary pump-probe techniques, namely, spin-, energy-, and time-resolved photoemission and the time-resolved magneto-optical Kerr effect. Combining the two methods, it is possible to identify the microscopic electron spin-flip mechanisms responsible for the ultrafast macroscopic magnetization dynamics of the cobalt film. In particular, we show that electron-magnon excitation does not affect the overall magnetization even though it is an efficient spin-flip channel on the sub-200 fs time scale. Instead, we find experimental evidence for the relevance of Elliott-Yafet-type spin-flip processes for the ultrafast demagnetization taking place on a time scale of 300 fs. 相似文献
76.
Rueff JP Itié JP Taguchi M Hague CF Mariot JM Delaunay R Kappler JP Jaouen N 《Physical review letters》2006,96(23):237403
We report on the most complete investigation to date of the -electron properties at the transition in elemental Ce by resonant inelastic x-ray scattering (RIXS). The Ce 2p3d-RIXS spectra were measured directly in the bulk material as a function of pressure through the transition. The spectra were simulated within the Anderson impurity model. The occupation number n(f) and f double occupancy were derived from the calculations in both gamma and alpha phases in the ground state. We find that the electronic structure changes result mainly from band formation of 4f electrons which concurs with reduced electron correlation and increased Kondo screening at high pressure. 相似文献
77.
Herranz G Ranchal R Bibes M Jaffrès H Jacquet E Maurice JL Bouzehouane K Wyczisk F Tafra E Basletic M Hamzic A Colliex C Contour JP Barthélémy A Fert A 《Physical review letters》2006,96(2):027207
We report on tunneling magnetoresistance (TMR) experiments that demonstrate the existence of a significant spin polarization in Co-doped (La, Sr)TiO(3-delta) (Co-LSTO), a ferromagnetic diluted magnetic oxide system (DMOS) with high Curie temperature. These TMR experiments have been performed on magnetic tunnel junctions associating Co-LSTO and Co electrodes. Extensive structural analysis of Co-LSTO combining high-resolution transmission electron microscopy and Auger electron spectroscopy excluded the presence of Co clusters in the Co-LSTO layer and thus, the measured ferromagnetism and high spin polarization are intrinsic properties of this DMOS. Our results argue for the DMOS approach with complex oxide materials in spintronics. 相似文献
78.
Aniol KA Armstrong DS Averett T Benaoum H Bertin PY Burtin E Cahoon J Cates GD Chang CC Chao YC Chen JP Choi S Chudakov E Craver B Cusanno F Decowski P Deepa D Ferdi C Feuerbach RJ Finn JM Frullani S Fuoti K Garibaldi F Gilman R Glamazdin A Gorbenko V Grames JM Hansknecht J Higinbotham DW Holmes R Holmstrom T Humensky TB Ibrahim H de Jager CW Jiang X Kaufman LJ Kelleher A Kolarkar A Kowalski S Kumar KS Lambert D LaViolette P LeRose J Lhuillier D Liyanage N Margaziotis DJ Mazouz M McCormick K 《Physical review letters》2006,96(2):022003
We have measured the parity-violating electroweak asymmetry in the elastic scattering of polarized electrons from 4He at an average scattering angle = 5.7 degrees and a four-momentum transfer Q2 = 0.091 GeV2 . From these data, for the first time, the strange electric form factor of the nucleon G(E)s can be isolated. The measured asymmetry of A(PV) = (6.72 +/- 0.84(stat) +/- 0.21(syst) x 10(-6) yields a value of G(E)s = -0.038 +/- 0.042(stat) +/- 0.010(syst), consistent with zero. 相似文献
79.
In this contribution, we study several monocarbonyl-metal complexes in order to unravel the contribution of relativistic effects to the metal-ligand bond length and complexation energy. Using scalar density functional theory (DFT) constrained space orbital variation (CSOV) energy decomposition analysis supplemented by all-electron four-component DFT computations, we describe the dependency of relativistic effects on the orbitals involved in the complexation for the Au(+) isoelectronic series, namely, the fully occupied 5d orbitals and the empty 6s orbitals. We retrieve the well-known sensitivity of gold toward relativity. For platinum and gold, the four-component results illustrate the simultaneous relativistic expansion of the 5d orbitals and the contraction of the 6s orbitals. The consequences of such modifications are evidenced by CSOV computations, which show the importance of both donation and backdonation within such complexes. This peculiar synergy fades away with mercury and thallium for which coordination becomes driven by the accepting 6s orbitals only, which makes the corresponding complexes less sensitive toward the relativistic effects. 相似文献
80.