Cu/ZnO and Cu/ZrO2 interactions studied by contact angle measurement with TEM

A technique of contact angle measurement was applied to the nano-scale oxide-supported metal particles. For Cu supported on ZnO and ZrO2 the angles were found to increase and the work of adhesion to decrease with increasing particle size. Such a trend is interpreted as an effect of negative contact line tension of 2.1 x 10(-9) J m(-1) and 1.0 x 10(-9) J m(-1) in the Cu/ZnO and Cu/ZrO2 system, correspondingly. For the small-sized Cu particles the apparent work of adhesion on ZnO support is higher than that on ZrO2.     

Anosovite-type v(3)o(5): a new binary oxide of vanadium

The reaction of either V(2)F(6)·4H(2)O or a mixture of 60 wt % VF(2)·4H(2)O and 40 wt % VF(3)·3H(2)O with a water-saturated gaseous mixture of 15-20 vol % hydrogen in argon leads to the formation of a new polymorph of V(3)O(5) crystallizing in the orthorhombic anosovite-type structure. Quantum-chemical calculations show that the anosovite-type structure is about 15 kJ/mol less stable than the corresponding monoclinic Magnéli phase. In addition, there are no imaginary modes in the phonon density of states, supporting the classification of the anosovite-type phase as a metastable V(3)O(5) polymorph. Susceptibility measurements down to 3 K reveal no hint for magnetic ordering.     

Influence of Calcination Conditions on Structural and Solid-State Kinetic Properties of Iron Oxidic Species Supported on SBA-15

Iron oxidic species supported on silica SBA-15 were synthesized with various iron loadings using two different Fe^III precursors. The effect of varying powder layer thickness during calcination on structural and solid-state kinetic properties of Fe_xO_y/SBA-15 samples was investigated. Calcination was conducted in thin (0.3 cm) or thick (1.3 cm) powder layer. Structural characterization of resulting Fe_xO_y/SBA-15 samples was performed by nitrogen physisorption, X-ray diffraction, and DR-UV/Vis spectroscopy. Thick powder layer during calcination induced an increased species size independent of the precursor. However, a significantly more pronounced influence of calcination mode on species size was observed for the Fe^III nitrate precursor compared to the Fe^III citrate precursor. Temperature-programmed reduction (TPR) experiments revealed distinct differences in reducibility and reduction mechanism dependent on calcination mode. Thick layer calcination of the samples obtained from Fe^III nitrate precursor resulted in more pronounced changes in TPR profiles compared to samples obtained from Fe^III citrate precursor. TPR traces were analyzed by model-dependent Coats-Redfern method and model-independent Kissinger method. Differences in solid-state kinetic properties of Fe_xO_y/SBA-15 samples dependent on powder layer thickness during calcination correlated with differences in iron oxidic species size.     

Spectral Response of a Stochastic Oscillator under Impacts

An approximate analytical procedure is presented to estimate theresponse spectrum of an oscillator with elastic impacts under a Gaussian whitenoise excitation. The proposed approach is based on a perturbation analysis ofthe problem and on the use of the stochastic averaging principle. The basicidea is to replace the initial system by a more regular system obtained byapproximating the nonlinear restoring force by a Chebychev polynomial, and thento construct for this regular system two approximations: one for the flowand one for the stationary distribution of the response amplitude. Ananalytical approximation of the response spectrum can then be derived fromthese results. Predictions from this analytical approximation are compared with corresponding digital simulation estimates and with the ones obtained from theconventional equivalent linearization method.     

New results on proton emission from odd-odd nuclei

⁷⁸Kr beams were used to bombard ⁵⁸Ni, ⁹²Mo and ⁹⁶Ru, producing three new, odd-odd, proton-emitting isotopes, ¹³⁰Eu, ^164mIr and ¹⁷⁰Au. Preliminary experimental and theoretical results will be presented in this paper. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: mahmud@ph.ed.ac.uk     

Coupled ab initio potential energy surfaces for the two lowest 2A′ electronic states of the C2H molecule

Realistic two-valued potential energy surfaces for the reaction C(³P) + CH(X²Π) → C₂ + H have been constructed from a set of high level ab initio data describing the first two ²A′ electronic states of the C₂H system. These states have linear equilibrium configurations, known as the X ²Σ⁺ and A²Π states, and are coupled by a conical intersection. They lead to the formation of C₂(X¹Σ⁺ _g) and C₂(a³Π_u) considering an adiabatic dissociation process. The ab initio calculations are of the multireference configuration interaction variety and were carried out using a polarized triple-zeta basis set. Using the ab initio adiabatic energies and the matrix elements of the dipole moment, a 2 × 2 diabatic representation of the electronic Hamiltonian was built. Each element of this Hamiltonian matrix was expressed within the double many-body expansion (DMBE) scheme which is based, in this case, on the extended Hartree-Fock approximate correlation energy model (EHFACE). The analytical adiabatic potential energy surfaces are then obtained as the eigenvalues of this matrix, and display correctly the Σ/Π conical intersection. Moreover, the non-adiabatic couplings given by our analytical model are compared with the ab initio ones, and good qualitative agreement is observed.     

Quark gluon scattering at higher orders in QCD

The infrared evolution equation which sums up leading logarithmic terms is solved for the partonic reactionqgqX in the elastic case i.e.M _X0. The results of the exactO( _s ³ ) calculation are reproduced.     

Bixbyite-type V2O3--a metastable polymorph of vanadium sesquioxide

A metastable polymorph of vanadium sesquioxide was prepared by the reaction of vanadium trifluoride with a water-saturated gaseous mixture of 10 vol % hydrogen in argon. The new polymorph crystallizes in the bixbyite-type structure. At temperatures around 823 K a transformation to the well-known corundum-type phase is observed. Quantum-chemical calculations show that the bixbyite-type structure is about 9 kJ/mol less stable than the known corundum-based one. This result, in combination with the absence of imaginary modes in the phonon density of states, supports the classification of the bixbyite-type phase as a metastable V(2)O(3) polymorph. At ~50 K a paramagnetic to canted antiferromagnetic transition is detected.