Photoionization resonance in Cr(CO)6: implications for bonding of adsorbed CO

The partial photoionization cross sections of the valence levels of Cr(CO)₆ are reported in the photon energy range of 30 to 100 eV. The 4_o derived level shows a resonance at ≈ 18 eV kinetic energy. This resonance is well understood and has been seen in gas phase CO at 12 eV kinetic energy and in CO adsorbed on Ni(100) at 20 eV kinetic energy. The Cr(CO)₆ data show that the large shift in the kinetic energy of the resonance in adsorbed CO is due to potential changes upon bonding, not changes in the C to O distance. This resonance is not observed in the Cr(CO)₆ energy levels derived from the CO 5_o level. Calculations of the initial and final wavefunctions are presented to explain the sensitivity of the resonance in the 5_o level to bonding.     

Microdeformation in Poly-L-lactide and Poly-L-lactide + Hydroxyapatite Nanocomposite Thin Films

In order to gain new insight into failure mechanisms in poly-L-lactide (PLLA) and PLLA + hydroxyapatite nanocomposites, transmission electron microscopy has been used to investigate room temperature microdeformation in electron transparent thin films of these materials subjected to various heat treatments and deformed in tension using the “copper grid” technique. In amorphous PLLA the dominant microdeformation mechanism was crazing. Localized fibrillar deformation zones (DZs) were also observed in semicrystalline films, tending to propagate in regions where the lamellar trajectories were at high angles to the tensile axis. Thus, in spherulitic films, in which the lamellae formed well-defined stacks with approximately straight trajectories at the scale of the spherulite radii, individual DZs were observed to propagate over relatively large distances, as in the amorphous films. On the other hand, films cold crystallized by heating from the glassy state showed more homogeneous lamellar textures. These were associated with a relatively high density of low aspect ratio DZs. Addition of well dispersed nanosized hydroxyapatite (nHA) to the amorphous PLLA films was also found to result in an increase in the craze density, attributed to stress concentrations associated with void formation at the PLLA-particle interfaces during deformation. However, interpretation was less straightforward in cold crystallized PLLA + nHA thin films, owing to a correlation between the lamellar texture and the nHA particles. In this case, both void formation and favorable lamellar orientations may have contributed to initiation of the DZs in the vicinity of the particles. The results are argued to be broadly consistent with previous observations of the behavior of bulk PLLA and PLLA + nHA films with a range of microstructures, in which there was evidence for an improvement in ductility in the presence of the nHA, again attributed to voiding at the PLLA-particle interfaces.     

Isomechanical groups in bulk metallic glasses

Isomechanical groups are, as defined by Frost and Ashby [H.J. Frost and M.F. Ashby, Deformation–Mechanism Maps, Pergamon Press, Oxford, 1982], separate classes of materials that exhibit similar deformation and transport properties when normalised by an appropriate parameter. Fundamentally, this separation results from significant differences in material structure and bonding. Here, such an analysis is applied to 40 bulk metallic glasses (BMGs) grouped into three classes according to their Poisson's ratio, which is known to be an indicator of intrinsic toughness. Through rigorous statistical analysis, it is found that isomechanical groups are present and that they may result from (1) variation in the tendency for directional bonding, and (2) how liquid-like the structure is, which may be characterised by a quantification of local volumetric strain. These results suggest that, although experimentally observed properties from BMGs in different isomechanical groups are all typically considered within the same framework, differences in atomic packing and inter-atomic bonding mean that they should in fact be treated separately. These fundamental differences in bonding and structure may explain the known large variation in the tendency for toughness and plasticity in BMGs.     

Deformation and entanglement in semicrystalline polymers

Transmission electron microscopy (TEM) of amorphous and semicrystalline isotactic polystyrene (iPS) thin films deformed well below T _g, suggests the same crazing mechanism to operate in both cases. Therefore, by analogy with the amorphous case, highly entangled semicrystalline polymers, such as poly(ether ether ketone) (PEEK) should craze less readily in the glassy-semicrystalline state than iPS, which has a low degree of entanglement. Since this is confirmed by observation, it is reasonable to extend this analogy, and invoke entanglement in order to account for the high fracture resistance of highly entangled semicrystalline polymers, such as polyoxymethylene, using models previously applied to glassy amorphous polymers. There are nevertheless often significant decreases in fracture toughness in polyoxymethylene as the crystallization temperature is raised and/or the molecular weight is reduced, which we attribute to entanglement loss during lamellar folding.     

A pair of forbidden subgraphs and perfect matchings in graphs of high connectivity

Sumner [7] proved that every connected K _1,3-free graph of even order has a perfect matching. He also considered graphs of higher connectivity and proved that if m ≥ 2, every m-connected K _1,m+1-free graph of even order has a perfect matching. In [6], two of the present authors obtained a converse of sorts to Sumner’s result by asking what single graph one can forbid to force the existence of a perfect matching in an m-connected graph of even order and proved that a star is the only possibility. In [2], Fujita et al. extended this work by considering pairs of forbidden subgraphs which force the existence of a perfect matching in a connected graph of even order. But they did not settle the same problem for graphs of higher connectivity. In this paper, we give an answer to this problem. Together with the result in [2], a complete characterization of the pairs is given.     

Evidence for the distortion of C2H4 and C2H2 chemisorbed on W(100)

The adsorption of C₂H₄ on W(100) has been studied by ultraviolet photoelectron spectroscopy with hν = 21.22 eV. The spectrum measured after in initial saturation exposure at 80 K exhibits structure which correlates well with energy levels recently calculated by Demuth and Eastman (DE) for sp³ rehybridized C₂H₄. Dehydrogenation of the adsorbate, either by subsequent heating to 295 K or direct adsorption at 295 K, yields a spectrum which correlates with DE's calculation for sp² rehybridized C₂H₂. These results suggest that C₂H₄ and C₂H₂ may be distorted from their planar and linear structures respectively and that the CC bonds on these molecules are stretched by adsorption on W(100). Qualitative arguments suggest that the bonding site for both melecules is directly over a W atom and that the Dewar—Chatt model for πd bonding in organometallic compounds is applicable.     

Synthesis of Benz[1,2-a]aceanthrylene from Triptycene via Flash Vacuum Thermolysis

Benz[1,2-a]aceanthrylene is prepared from triptycene in 60 % yield by flash vacuum thermolysis at 875° C.     

A Note on Cyclic Connectivity and Matching Properties of Regular Graphs

In this paper info cyclic connectivity is studied in relation to certain matching properties in regular graphs. Results giving sufficient conditions in terms of cyclic connectivity for regular graphs to be factor-critical, to be 3-factor-critical, to have the restricted matching properties E(m, n) and to have defect-d matchings are obtained.