PubMed · 12876565
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Christoph E Nebel. 2003. Semiconductor materials: From gemstone to semiconductor.. https://doi.org/10.1038/nmat935
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The electronic origins of the magnetic signatures of [Fe(2)O(2)(5-Et(3)-TPA)(2)](ClO(4))(3), where 5-Et(3)-TPA = tris(5-ethyl-2-pyridylmethyl)amine, were investigated by density functional calculations. These signatures consist of a near-axial EPR spectrum, anisotropic superhyperfine broadening upon (17)O substitution in the Fe(2)O(2) core, and an unusually large, positive zero-field splitting parameter, D = 38 +/- 3 cm(-1). Density functional calculations identify the anisotropic (17)O superhyperfine broadening to be due to a preponderance of oxo 2p density perpendicular to the plane of the Fe(2)O(2) core in the three singly occupied molecular orbitals of the S = (3)/(2) ground state. The near-axial g-matrix arises from DeltaS = 0 spin-orbit mixing between the singly and doubly occupied d(pi) orbitals of the iron d-manifold. The large D is due to DeltaS = +/-1 spin-orbit mixing with low-lying d(pi) excited states. These experimental observables reflect the dominance of iron-oxo (rather than Fe-Fe) bonding in the Fe(2)O(2) core, and define the low-lying valence orbitals responsible for reactivity.
Carbon K ultrasoft x-rays (278 eV) interact with biological material producing random, isolated tracks of single electrons with a range < 7 nm (cf width of DNA helix approximately2 nm). The electron tracks produced by these ultrasoft x-rays are similar to the numerous secondary electrons and 'track ends' produced by essentially all ionizing radiations. They therefore provide a unique tool in the study of mechanisms of radiation action in the cell. Conventional carbon targets used with the Medical Research Councils cold-cathode discharge tubes have a limited lifetime of 40-50 min. We have investigated the use of thin, freestanding diamond films produced using chemical vapour deposition techniques as a new transmission target for a cold-cathode tube. We present here a novel use of diamond to produce CK ultrasoft x-rays for irradiation purposes. The system described produces an entrance absorbed dose rate to attached cells of approximately 0.2 Gy min(-1) which due to the long target lifetime is usable for low dose-rate CK x-ray studies.
The effects of hydrostatic pressure upon (1) a segmented poly (ester urethane), (2) a hydrolytically degraded sample of the same polymer, and (3) models for the polyurethane and polyester segments in this polymer have been studied by Fourier transform infrared spectroscopy using high-pressure diamond anvil cells (DACs). The pressure responses of the vibrational frequencies of specific functional groups of the poly (ester urethane) in the 0-100-kbar range are compared with data for individual segment models and the partially degraded sample. The results indicated that the polymer is highly stable in this pressure regime, with no measurable degradation or phase changes. Differences in the pressure dependency of specific infrared bands between the poly (ester urethane) sample and the partially degraded sample are slight and consistent with changes in hydrogen-bonding interactions and shorter chain lengths in the degraded sample.