Size-dependent pressure-induced amorphization in nanoscale TiO2

We investigated the size-dependent high-pressure phase transition behavior of nanocrystalline anatase TiO2 with synchrotron x-ray diffraction and Raman spectroscopy to 45 GPa at ambient temperature. Pressure-induced amorphization results in a high-density amorphous (HDA) form when the starting crystallite size is < 10 mm. The HDA-TiO2 transforms to a low-density amorphous form at lower pressures. Harnessing the nanometer length scale thus provides a new window for experimental investigation of amorphization in poor glass formers and a synthesis route for new amorphous materials.     

More on shear modulus collapse of lattices at high pressure

In his recent paper, Shear modulus collapse of lattices at high pressure, J. Phys. Cond. Matt. 16 (2004) L125, V.V. Kechin claims that the zero temperature shear modulus of a metallic solid vanishes at a high critical pressure, and the critical pressures for this shear modulus collapse lie in the range 0-250 Mbar for elemental metals. Here we demonstrate that Kechin's arguments contain an erroneous assumption, and therefore, do not prove that all metals become mechanically unstable at high pressures. Ab initio calculations and experimental results on a number of solids are analyzed to confirm our conclusion.     

UV photolysis products of propiolic acid in noble-gas solids

Photolysis (193 nm) of propiolic acid (HCCCOOH) was studied with Fourier transform infrared spectroscopy in noble-gas (Ar, Kr, and Xe) solid matrixes. The photolysis products were assigned using ab initio quantum chemistry calculations. The novel higher-energy conformer of propiolic acid was efficiently formed upon UV irradiation, and it decayed back to the ground-state conformer on a time scale of approximately 10 min by tunneling of the hydrogen atom through the torsional energy barrier. In addition, the photolysis produced a number of matrix-isolated 1:1 molecular complexes such as HCCH...CO2, HCCOH...CO, and H2O...C3O. The HCCH...CO2 complex dominated among the photolysis products, and the computations suggested a parallel geometry of this complex characterized by an interaction energy of -9.6 kJ/mol. The HCCOH...CO complex also formed efficiently, but its concentration was strongly limited by its light-induced decomposition. In this complex, the most probable geometry was found to feature the interaction of carbon monoxide with the OH group via the carbon atom, and the computational interaction energy was determined to be -18.3 kJ/mol. The formation of the strong H2O...C3O complex (interaction energy -21 kJ/mol) was less efficient, which might be due to the inefficiency of the involved radical reaction.     

Virtual Eigenvalues of the High Order Schrödinger Operator II

We consider the Schr?dinger operator H_γ = ( − Δ)^l + γ V(x)· acting in the space where 2l ≥ d, V (x) ≥ 0, V (x) is continuous and is not identically zero, and We study the asymptotic behavior as of the non-bottom negative eigenvalues of H_γ, which are born at the moment γ = 0 from the lower bound λ = 0 of the spectrum σ(H₀) of the unperturbed operator H₀ = ( − Δ)^l (virtual eigenvalues). To this end we use the Puiseux-Newton diagram for a power expansion of eigenvalues of some class of polynomial matrix functions. For the groups of virtual eigenvalues, having the same rate of decay, we obtain asymptotic estimates of Lieb-Thirring type.     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.     

Sensitivity of the Lanczos recurrence to Gaussian quadrature data: How malignant can small weights be?

Stability of passing from Gaussian quadrature data to the Lanczos recurrence coefficients is considered. Special attention is paid to estimates explicitly expressed in terms of quadrature data and not having weights in denominators. It has been shown that the recent approach, exploiting integral representation of Hankel determinants, implies quantitative improvement of D. Laurie’s constructive estimate.It has also been demonstrated that a particular implementation on the Hankel determinant approach gives an estimate being unimprovable up to a coefficient; the corresponding example involves quadrature data with a small but not too small weight. It follows that polynomial increase of a general case upper bound in terms of the dimension is unavoidable.     

Ferromagnetism of Fractal Hierarchy Dissipative Structures Based on Metalcontaining Heteroaromatic Systems

Abstract

Fractal hierarchy dissipative structures (FHDS) can quite possibly manifest new non-phonon type of magnetic ordering. In this paper we formulate the principles of FHDS formation from microscopic to macroscopic levels, determine physico-chemical criteria for picking up a suitable heteroaromatic system as well as the type of metal to obtain fractal ferromagnetism. Conditions of fractal ferromagnetism existance can be deduced from the Stoner's criterion of ferromagnetism in Hubbard model applied to fractal geometry.     

A black-box rational Arnoldi variant for Cauchy–Stieltjes matrix functions

Rational Arnoldi is a powerful method for approximating functions of large sparse matrices times a vector. The selection of asymptotically optimal parameters for this method is crucial for its fast convergence. We present and investigate a novel strategy for the automated parameter selection when the function to be approximated is of Cauchy–Stieltjes (or Markov) type, such as the matrix square root or the logarithm. The performance of this approach is demonstrated by numerical examples involving symmetric and nonsymmetric matrices. These examples suggest that our black-box method performs at least as well, and typically better, as the standard rational Arnoldi method with parameters being manually optimized for a given matrix.     

On Influence of Contranormal Subgroups on the Structure of Infinite Groups

Following Rose, a subgroup H of a group G is called contranormal, if G = H ^G . In certain sense, contranormal subgroups are antipodes to subnormal subgroups. It is well known that a finite group is nilpotent if and only if it has no proper contranormal subgroups. However, for the infinite groups this criterion is not valid. There are examples of non-nilpotent infinite groups whose subgroups are subnormal; in paricular, these groups have no contranormal subgroups. Nevertheless, for some classes of infinite groups, the absence of contranormal subgroups implies the nilpotency of the group. The current article is devoted to the search of such classes. Some new criteria of nilpotency in certain classes of infinite groups have been established.