Electron microscopic investigation of the molecular mechanism of plastic deformation of polyethylene and isotactic polystyrene crystals

The molecular process involved in the plastic deformation of crystals of linear polyethylene and isotactic polystyrene by necking was investigated by transmission electron microscopy (TEM). The results for the draw ratio, the height, and the shape of the neck and the molecular structure of the deformed material suggest that plastic deformation occurs basically by the unfolding and bending of the molecules in a deformation region only a few nm wide. The observations are at variance with deformation models involving complete unfolding of the molecules or the breaking off of folded-chain blocks and the incorporation of these blocks into the deformed material.     

An efficient step size control for continuation methods

In solving a nonlinear equation by the use of a continuation method one of the crucial problems is the choice of the step sizes. We present a model for the total computational cost of a standard numerical continuation process and solve the problem of optimal step size control for this model. Using the theoretical results as a basis, we develop an adaptive step size algorithm for Newton's method. This procedure is computationally inexpensive and it gives quite satisfactory results compared to some other numerical experiments found in the literature.     

Application of non-equilibrium thermodynamics to problems of thermal analysis

On the basis of non-equilibrium thermodynamics, the kinetic equations of thermal analysis are derived for several important chemical consecutive and concurrent reactions. These equations are solved analytically and numerically and the obtained solutions are discussed. Hereby hints are obtained for the further development of thermal methods. It is shown that, in most cases, the kinetics of coupled chemical reactions can only be determined with special selective methods.     

Ecophysiological Studies on the Vegetation of Madagascar: A δ13C and δD Survey for Incidence of Crassulacean Acid Metabolism (Cam) Among Orchids From Montane Forests and Succulents from the Xerophytic Thorn-Bush

Abstract

The incidence of Crassulacean acid metabolism (CAM) in plants collected at various habitats in Madagascar was investigated by survey of carbon and hydrogen isotope ratios ((δ¹³C and δD values). In about 50% of the epiphytic orchids from evergreen higher and lower montane forests the δ¹³C values were indicative for CAM. The remainder of the species are presumably C₃ plants. In all samples of malagasy epiphytic leafless orchids comprising 9 species, the δ¹³C values suggest extreme CAM with CO₂ uptake proceeding entirely during the night. All terrestrial orchids collected in the lower montane forests obviously acquire external carbon by C₃-photosynthesis, whereas Lissochilus decaryi, a terrestrial orchid from the semi-arid south of Madagascar and various other species of this genus are CAM plants. This is the first report of CAM occurrence in sympodial terrestrial orchids.

Judged by the δ¹³C values, all succulents (mainly Didiereaceae, Euphorbiaceae, Crassulaceae and Asclepiadaceae) collected at the xerophytic thorn-bush of the semi-arid south perform pronounced CAM. Where it applies, our δ¹³C measurements in the thorn-bush succulents revealed values being practically identical with those found by K. Winter in samples of the same species collected at the same site nearly 10 years earlier. This shows extreme constancy over long duration of time in the mode of CAM performed by the succulents of the malagasy thorn-bush vegetation. Since the δ¹³C survey now comprises all 11 known species of the Didiereaceae, it is unequivocally clear that all members of this family are CAM plants. Most of the individuals of the species of the Didiereaceae grown in a glass-house had slightly more negative δ¹³C values compared with those grown at the natural stands suggesting some contribution of C₃-photosynthesis to carbon acquisition under the evaporatively less demanding glass-house conditions (and perhaps higher CO₂ concentrations in the gas phase).

Despite of the fact that the hydrogen isotope composition of meteoric waters depends to a large extent on the altitude and temperature-climate of the site where the concerned plants grow, it was found that in samples obtained in the cooler higher evergreen montane forest as well as in the warmer lower evergreen montane forest and the lowland thorn-bush of the hot, semiarid south of Madagascar the δ values found in the organic matter (δD^org) were in the same range (between about - 10‰ to about - 90‰). This suggests that in our case the hydrogen isotope compositions of the meteoric waters were of minor importance in bringing about the δD^org values found in the plants.     

Determination of spin,magnetic moment and isotopic shift of neutron rich205Hg by optical pumping

Neutron rich²⁰⁵Hg (T _1/2=5.2 min) was produced and on-line mass separated at the ISOLDE facility at CERN. The polarization achieved by optical pumping via the atomic line (6s ²¹ S ₀?6s6p ³ P ₁,λ=2 537Å) was monitored by theβ decay asymmetry. Hyperfine structure and isotopic shift of the²⁰⁵Hg absorption line was determined by Zeeman scanning. In addition a magnetic resonance was performed on the polarized²⁰⁵Hg nuclei in the atomic ground state. The results are: \(I(^{205} Hg) = \tfrac{1}{2}\) (confirmed);μ _I (²⁰⁵Hg)=0.5915 (1)μ _N (uncorrected for diamagnetism); isotopic shiftδv^204/205=v(²⁰⁵Hg)-v(204Hg)=?1.8 (1) GHz.μ _I and IS are discussed briefly in the frame of current literature.     

Alkylthio bridged 44 cve triangular platinum clusters: synthesis, oxidation, degradation, ligand substitution, and quantum chemical calculations

Acetylplatinum(II) complexes trans-[Pt(COMe)Cl(L)2] (L = PPh3, 2a; P(4-FC6H4)3, 2b) were found to react with dialkyldisulfides R2S2 (R = Me, Et, Pr, Bu; Pr = n-propyl, Bu = n-butyl), yielding trinuclear 44 cve (cluster valence electrons) platinum clusters [(PtL)3(mu-SR)3]Cl (4). The analogous reaction of 2a-b with Ph2S2 gave SPh bridged dinuclear complexes trans-[{PtCl(L)}2(mu-SPh)2] (5), whereas the addition of Bn2S2 (Bn = benzyl) to 2a ended up in the formation of [{Pt(PPh3)}3(mu3-S)(mu-SBn)3]Cl (6). Theoretical studies based on the AIM theory revealed that type 4 complexes must be regarded as triangular platinum clusters with Pt-Pt bonds whereas complex 6 must be treated as a sulfur capped 48 ve (valence electrons) trinuclear platinum(II) complex without Pt-Pt bonding interactions. Phosphine ligands with a lower donor capability in clusters 4 proved to be subject to substitution by stronger donating monodentate phosphine ligands (L' = PMePh2, PMe2Ph, PBu3) yielding clusters [(PtL')3(mu-SR)3]Cl (9). In case of the reaction of clusters 4 and 9 with PPh2CH2PPh2 (dppm), a fragmentation reaction occurred, and the complexes [(PtL)2(mu-SMe)(mu-dppm)]Cl (12) and [Pt(mu-SMe)2(dppm)] (13) were isolated. Furthermore, oxidation reactions of cluster [{Pt(PPh3)}3(mu-SMe)3]Cl (4a) using halogens (Br2, I2) gave dimeric platinum(II) complexes cis-[{PtX(PPh3)}2(mu-SMe)2] (14, X = Br, I) whereas oxidation reactions using sulfur and selenium afforded chalcogen capped trinuclear 48 ve complexes [{Pt(PPh3)}3(mu3-E)(mu-SMe)3] (15, E = S, Se). All compounds were fully characterized by means of NMR and IR spectroscopy, microanalyses, and ESI mass spectrometry. Furthermore, X-ray diffraction analyses were performed for the triangular cluster 4a, the trinuclear complex 6, as well as for the dinuclear complexes trans-[{Pt(AsPh3)}2(mu-SPh)2] (5c), [{Pt(PPh3)}2(mu-SMe)(mu-dppm)]Cl (12a), and [{{PtBr(PPh3)}2(mu-SMe)2] (14a).     

Integration of electron density and molecular orbital techniques to reveal questionable bonds: the test case of the direct Fe-Fe bond in Fe2(CO)9

The article illustrates the advantages of partitioning the total electron density rho(rb), its Laplacian (inverted Delta)2 rho(rb), and the energy density H(rb) in terms of orbital components. By calculating the contributions of the mathematically constructed molecular orbitals to the measurable electron density, it is possible to quantify the bonding or antibonding character of each MO. This strategy is exploited to review the controversial existence of direct Fe-Fe bonding in the triply bridged Fe2(CO)9 system. Although the bond is predicted by electron counting rules, the interaction between the two pseudo-octahedral metal centers can be repulsive because of their fully occupied t(2g) sets. Moreover, previous atoms in molecules (AIM) studies failed to show a Fe-Fe bond critical point (bcp). The present electron density orbital partitioning (EDOP) analysis shows that one sigma bonding combination of the t(2g) levels is not totally overcome by the corresponding sigma* MO, which is partially delocalized over the bridging carbonyls. This suggests the existence of some, albeit weak, direct Fe-Fe bonding.     

Accurate masses of unstable rare-earth isotopes by ISOLTRAP

Direct mass measurements of neutron-deficient rare-earth isotopes in the vicinity of ¹⁴⁶Gd were performed with the Penning trap mass spectrometer ISOLTRAP at ISOLDE/CERN. This paper reports on the measurement of more than 40 isotopes of the elements praseodymium, neodymium, promethium, samarium, europium, dysprosium and holmium, that have been measured with a typical accuracy of m 14 keV. An atomic mass evaluation has been performed taking into account other experimental mass values via a least-squares adjustment. The results of the adjustment are discussed. Received: 18 April 2000 / Accepted: 12 July 2000     

Experimental test of special relativity by laser spectroscopy

The Doppler-free laser-spectroscopic frequency measurement of Doppler-shifted optical lines in forward and backward direction of a fast ion beam permits a sensitive test of the relativistic Doppler-formula and, hence, the relativistic time dilation factor . An experiment on metastable ⁷Li⁺, stored at a velocity of v = 0.064c in the Heidelberg heavy-ion storage ring TSR, has confirmed time dilation with unprecedented accuracy. Latest tests at two different ion-velocities (v = 0.03c and v = 0.064c) will enhance these measurements. An improved version of this experiment will be carried out at the experimental storage ring (ESR) at the Gesellschaft für Schwerionenforschung (GSI) in Darmstadt. The ESR permits ⁷Li⁺ to be stored at v = 0.33c which promises an improvement of the sensitivity to deviations from γ _SR by an order of magnitude. A first test at the ESR has shown the feasibility for this kind of experiment.