Local adsorption sites and bondlength changes in Ni(1 0 0)/H/CO and Ni(1 0 0)/CO

The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding.     

Influence of isovalent substitutions on absorption spectra of orthoferrities

The role of impurity ions in formation of the optical properties of rare-earth orthoferrites is investigated. Optical spectra of the substituted against unsubstituted orthoferrites are presented. The influence of different isovalent substitutions on the optical absorption of orthoferrites that are promising for magnetooptics is studied. Institute of Solid-State and Semiconductor Physics of the Academy of Sciences of Belarus, 17, P. Brovka St., Minsk, 220072, Belarus. Translated from zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 642–645, September–October, 1997.     

Fluorination of diamond — C4F9I and CF3I photochemistry on diamond (100)

The radiation-induced decomposition of C₄F₉I and CF₃I overlayers at 119 K on diamond (100) surfaces has been shown to be an efficient route to fluorination of the diamond surface. X-ray photoelectron spectroscopy has been used for photoactivation as well as for studying the photodecomposition of the fluoroalkyl iodide molecules, the attachment of the photofragments to the diamond surface, and the thermal decomposition of the fluoroalkyl ligands. Measured chemical shifts agree well with ab initio calculations of both C 1s and F 1s binding energies. It is found that chemisorbed CF₃ groups on diamond (100) decompose by 300 K whereas C₄F₉ groups decompose over the range 300 to 700 K and this reactivity difference is rationalized on steric grounds. Both of these thermal decomposition processes produce surface C---F bonds on the diamond. The surface C---F species thermally decompose over a wide temperature range extending up to 1500 K. Hydrogen passivation of the diamond surface is ineffective in preventing free radical attack from the photodissociated products of the fluoroalkyl iodides; I atoms produced photolytically abstract H from surface C---H bonds to yield hydrogen iodide at 119 K allowing diamond fluorination. The attachment of chemisorbed F species to the diamond (100) surface causes band bending as the surface states are occupied as a result of chemisorption. This results in a shift to higher binding energy of the diamond-related C 1s levels present in the surface and subsurface regions which are sampled by XPS on the diamond. The use of photoactivation of fluoroalkyl iodides for the fluorination of diamond surfaces provides a convenient route compared to other methods involving the action of atomic F, molecular F₂, XeF₂ and F-containing plasmas.     

THERMAL AND THERMO-ELASTIC-PLASTIC RESPONSE OF CERAMIC-METAL FUNCTIONALLY GRADED MATERIALS—THERMAL SHOCK PROBLEM

The thermal and thermo-elastic-plastic response of newly developed ceramic-metalfunctionally graded materials under a thermal shock load is studied.The materials are heated at the ce-ramic surface with a sudden high-intensity heat flux input,and cooled at the metal surface with aflowing liquid nitrogen.Emphasis is placed on two aspects:(1)the influence of the graded composi-tion of the materials on the temperature and stress response;and(2)the optimum design of the gradedcomposition from a unified viewpoint of the heat insulation property and stress relaxation property.Moreover,a comparison between the thermoelastic stress and the thermo-elastic-plastic stress is alsomade to indicate the plasticity effect.     

MO analysis of macroscopic supercurrent flow in MgB 2

We present results from an extended magneto-optical (MO) analysis of two samples cut from high-density pellets of MgB₂. The first sample was studied in order to show that no matter how large the sample is and despite the bulk granularity, the material enters into a critical state in a crystal-like fashion. The second sample was chosen for the quantitative analysis. A numerical approach based on an inverted 2D Biot-Savart model was used to calculate the current paths across the homogeneous polycrystalline bulk, as well as in the vicinity and across some morphological defects. Local current densities in the homogeneous part were estimated as a function of the applied magnetic field at different temperatures, in three regimes: below full penetration, at full penetration and above full penetration, respectively. A hypothesis of interpretation of the apparent absence of magnetic granularity inside the polycrystalline microstructure is presented. It is related to a critical state likely reached by a network of strongly coupled Josephson junctions. Received 31 May 2001 and Received in final form 5 December 2001     

Crystal structure and magnetic ordering of RNi Si compounds

The element distributions and the magnetic ordering behaviour of compounds RNi₁₀Si₂ (R = Tb, Dy, Ho, Er, Tm) have been studied by neutron powder diffraction down to temperatures of 1.6 K. The compounds crystallize in an ordered variant of the ThMn₁₂ structure type in the tetragonal space group P4/nmm. An ordered 1:1 distribution of Ni and Si on sites 4d and 4e, respectively, corresponds to a modulation vector [0, 0, 1] with respect to the space group I4/mmm of the ThMn₁₂ structure. TbNi₁₀Si₂ orders antiferromagnetically below T _N = 4.5 K with a magnetic propagation vector of [0, 0, 1/2]. The magnetic Tb moments, 8.97(2) /Tb atom at 1.6 K, are aligned along the c-axis. The Ni sites in TbNi₁₀Si₂ do not carry any ordered magnetic moments. The compounds with R = Dy, Ho, Er, and Tm are paramagnetic down to 1.6 K and 3.0 K, respectively. Received 10 July 2002 / Received in final form 12 September 2002 Published online 29 October 2002     

On practical metrology and chemical analysis: etalons and traceability systems

 National measurement systems are infrastructures to ensure, for each nation, a consistent and internationally recognised basis for measurement. Such complex systems have historical, technical, legal, organisational and institutional aspects to connect scientific metrology with practical measurements. Underlying any valid measurement is a chain of comparisons linking the measurement to an accepted standard. The ways the links are forged and the etalons (measurement standards) to which they connect are defining characteristics of all measurement systems. This is often referred to as traceability which aims at basing measurements in common measurement units – a key issue for the integration of quantitative chemical analysis with the evolving physical and engineering measurement systems. Adequate traceability and metrological control make possible new technical capabilities and new levels of quality assurance and confidence by users in the accuracy and integrity of quantitative analytical results. Traceability for chemical measurements is difficult to achieve and harder to demonstrate. The supply of appropriate etalons is critical to the development of metrology systems for chemical analysis. An approach is suggested that involves the development of networks of specialised reference laboratories able to make matrix-independent reference measurements on submitted samples, which may then be used as reference materials by an originating laboratory using its practical measurement procedures. Received: 31 July 1995 Accepted: 19 August 1995     

Shape transition from InAs quantum dash to quantum dot on InP(3 1 1)A

We report on the shape transition from InAs quantum dashes to quantum dots (QDs) on lattice-matched GaInAsP on InP(3 1 1)A substrates. InAs quantum dashes develop during chemical-beam epitaxy of 3.2 monolayers InAs, which transform into round InAs QDs by introducing a growth interruption without arsenic flux after InAs deposition. The shape transition is solely attributed to surface properties, i.e., increase of the surface energy and symmetry under arsenic deficient conditions. The round QD shape is maintained during subsequent GaInAsP overgrowth because the reversed shape transition from dot to dash is kinetically hindered by the decreased ad-atom diffusion under arsenic flux.     

The Systematics of Muonium Hyperfine Constants

The hyperfine constants for muonium in elemental and binary inorganic solids suggest formation of three different families of defect centre, with distinct electronic structures. The overall range of values, spanning nearly five orders of magnitude, and their correlation with host properties such as band gap and electron affinity, reveal a deep-to-shallow instability which has profound implications for the electrical properties of hydrogen impurity in electronic materials, both semiconducting and dielectric.     

Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.