Photoexcitation and ionization in molecular oxygen: Theoretical studies of electronic transitions in the discrete and continuous spectral intervals

Theoretical studies of valence-electron (1πg, 1πu, 3σg) photoexcitation and ionization cross sections in molecular oxygen are reported employing separated-channel static-exchange calculations and the Stieltjes–Tchebycheff moment-theory technique. As in previously reported investigations of photoexcitation and ionization in small molecules following this approach, canonical Hartree–Fock orbitals, large Gaussian basis sets, and many-electron eigenstates of correct symmetry are used in defining appropriate noncentral static-exchange potentials and in computations of the appropriate discrete and continuum transition strengths. It is particularly important in molecular oxygen to incorporate the appropriate ionic parentages of the various photoionization multiplet states in order to obtain the correct partial-channel cross sections. The calculated discrete series associated with 1πg excitation are found to be in good agreement with available experimental assignments and previously reported theoretical studies, and the predicted states associated with 1πu and 3σg excitations are in general accord with assignments for the higher series based on spectral and quantum-defect analysis. Although the observed photoelectron spectra and photoionization cross sections are relatively complex, the calculated total vertical electronic photoabsorption cross section and the partial-channel photoionization cross sections for production of X 2πg, a 4πu, A 2πu, 2 2πu, 3 3IIu, b 4∑g-, and B 2∑g-, ionic states are found to be in good accord with recent synchrotron radiation, line-source, electron-impact, and (e,2e) dipole oscillator-strength measurements when proper account is taken of the parentages of the various multiplet states. The partial-channel cross sections exhibit resonancelike structures that can be attributed to contributions from diabatic valencelike virtual states that appear in the appropriate photoionization continua, rather that in the corresponding discrete spectral intervals. These features in the dipole spectrum of molecular oxygen are discussed and are contrasted and compared with the results of previously reported related studies in molecular nitrogen and carbon monoxide

Possible world-wide middle miocene iridium anomaly and its relationship to periodicity of impacts and extinctions

In a study of one million years of Middle Miocene sediment deposition in ODP Hole 689B in the Weddell Sea near Antarctica, a single iridium (Ir) anomaly of 44 (+ or - 10) x 10 to the 12th gram Ir per gram rock (ppt) was observed in core 6H, section 3, 50 to 60 cm, after background contributions associated with manganese precipitates and clay are subtracted. The ODP Hole 689B is 10,000 km away from another site, DSDP Hole 588B in the Tasman Sea north of New Zealand, where a single Ir anomaly of 144 + or - 7 ppt over a background of 11 ppt was found in an earlier study of 3 million years of deposition. From chemical measurements the latter deposition was thought to be impact-related. Ir measurements were made, following neutron activation, with the Iridium Coincidence Spectrometer. The age vs depth calibration curves given in the DSDP and ODP preliminary reports indicate the ages of the Iranomalies are identical, 11.7 million years, but the absolute and relative uncertainties in the curves are not known. Based on the newest age data the age estimate is 10 million years. As the Ir was deposited at the two sites at about the same time and they are one quarter of the way around the world from each other it seems likely that the deposition was world-wide. The impact of a large asteroid or comet could produce the wide distribution, and this data is supportive of the impact relationship deduced for Deep Sea Drilling Project (DSDP) 588B from the chemical evidence. If the surface densities of Ir at the two sites are representative of the world-wide average, the diameter of a Cl type asteroid containing the necessary Ir would be 3 + or - 1 km, which is large enough to cause world-wide darkness and hence extinctions although the latter point is disputed

The role played by the molecular weight and acetylation degree in modualting the stiffness and elasticity of chitosan gels

A broad library of chitosans was produced varying the molecular weight and the fraction of acetylated units, FA. The produced chitosans were used for the formation of wall-to-wall cylindrical gels through a controlled external gelation using tripolyphosphate (TPP) as cross-linker. The resulting gels were analyzed by rheometry. Viscosity average degree of polymerization (DPv\uaf)\u202f>\u202f152 was shown to be required for the formation of stable gels. Both gel stiffness and gel rupture strength were proportional to the molecular weight regardless of the applied deformation. Increasing acetylation produced a marked reduction of the shear modulus, but, in parallel, switched the networks from rigid and brittle to weak and elastic. Intriguingly, gels made of chitosan with FA\u202f=\u202f0.37 displayed notable elasticity, i.e. up to 90% of applied strain falls into linear regime. These findings suggest that the frequency of glucosamine (D unit) and N-acetyl-glucosamine (A unit) contribute to a subtle structure-property relationship in chitosan-TPP gels

Influence of uniaxial stress on the lamellar spacing of eutectics

Directional solidification of lamellar eutectic structures submitted to uniaxial stress is investigated. In the spirit of an approximation first used by Jackson and Hunt, we calculate the stress tensor for a two-dimensional crystal with triangular surface, using a Fourier expansion of the Airy function. crystal with triangular surface in contact with its melt, given that a uniaxial external stress is applied. The effect of the resulting change in chemical potential is introduced into the standard model for directional solidification of a lamellar eutectic. This calculation is motivated by an observation, made recently [I. Cantat, K. Kassner, C. Misbah, and H. M\"uller-Krumbhaar, Phys. Rev. E, in press] that the thermal gradient produces similar effects as a strong gravitational field in the case of dilute-alloy solidification. Therefore, the coupling between the Grinfeld and the Mullins-Sekerka instabilities becomes strong, as the critical wavelength of the former instability gets reduced to a value close to that of the latter. Analogously, in the case of eutectics, the characteristic length scale of the Grinfeld instability should be reduced to a size not extremely far from typical lamellar spacings. In a Jackson-Hunt like approach we average the undercooling, including the stress term, over a pair of lamellae. Following Jackson and Hunt, we assume the selected wavelength to be determined by the minimum undercooling criterion and compute its shift due to the external stress. we realize the shifting of the wavelength by the application of external stress. In addition, we find that in general the volume fraction of the two solid phases is changed by uniaxial stress. Implications for experiments on eutectics are discussed.Comment: 8 pages RevTex, 6 included ps-figures, accepted for Phys. Rev.

Guar gum/borax hydrogel: Rheological, low field NMR and release characterizations

Guar gum (GG) and Guar gum/borax (GGb) hydrogels are studied by means of rheology, Low Field Nuclear Magnetic Resonance (LF NMR) and model drug release tests. These three approaches are used to estimate the mesh size (ζ) of the polymeric network. A comparison with similar Scleroglucan systems is carried out. In the case of GGb, the rheological and Low Field NMR estimations of ζ lead to comparable results, while the drug release approach seems to underestimate ζ. Such discrepancy is attributed to the viscous effect of some polymeric chains that, although bound to the network to one end, can freely fluctuate among meshes. The viscous drag exerted by these chains slows down drug diffusion through the polymeric network. A proof for this hypothesis is given by the case of Scleroglucan gel, where the viscous contribution is not so significant and a good agreement between the rheological and release test approaches was found

Cell Activities on Viscoelastic Substrates Show an Elastic Energy Threshold and Correlate with the Linear Elastic Energy Loss in the Strain-Softening Region

Energy-sensing in viscoelastic substrates has recently been shown to be an important regulator of cellular activities, modulating mechanical transmission and transduction processes. Here, this study fine-tunes the elastic energy of viscoelastic hydrogels with different physical and chemical compositions and shows that this has an impact on cell response in 2D cell cultures. This study shows that there is a threshold value for elastic energy (≈0.15 J m−3) above which cell adhesion is impaired. When hydrogels leave the linear stress–strain range, they show softening (plastic) behavior typical of soft tissues. This study identifies a correlation between the theoretical linear elastic energy loss in the strain-softening region and the number of cells adhering to the substrate. This also has implications for the formation of vinculin-rich anchorage points and the ability of cells to remodel the substrate through traction forces. Overall, the results reported in this study support that the relationship between cell activities and energy-sensing in viscoelastic substrates is an important aspect to consider in the development of reliable ex vivo models of human tissues that mimic both normal and pathological conditions

Wetting layer thickness and early evolution of epitaxially strained thin films

We propose a physical model which explains the existence of finite thickness wetting layers in epitaxially strained films. The finite wetting layer is shown to be stable due to the variation of the non-linear elastic free energy with film thickness. We show that anisotropic surface tension gives rise to a metastable enlarged wetting layer. The perturbation amplitude needed to destabilize this wetting layer decreases with increasing lattice mismatch. We observe the development of faceted islands in unstable films.Comment: 4 pages, 3 eps figure

Crystal growth and elasticity

The purpose of this paper is to review some elasticity effects in epitaxial growth. We start by a description of the main ingredients needed to describe elasticity effects (elastic interactions, surface stress, bulk and surface elasticity, thermodynamics of stressed solids). Then we describe how bulk and surface elasticity affect growth mode and surface morphology by means of stress-driven instability. At last stress-strain evolution during crystal growth is reported.Comment: 12 page

Prepyramid-to-pyramid transition of SiGe islands on Si(001)

The morphology of the first three-dimensional islands appearing during strained growth of SiGe alloys on Si(001) was investigated by scanning tunneling microscopy. High resolution images of individual islands and a statistical analysis of island shapes were used to reconstruct the evolution of the island shape as a function of size. As they grow, islands undergo a transition from completely unfacetted rough mounds (prepyramids) to partially {105} facetted islands and then they gradually evolve to {105} facetted pyramids. The results are in good agreement with the predictions of a recently proposed theoretical model