What do we learn from the local geometry of glass-forming liquids?

We examine the local geometry of a simulated glass-forming polymer melt. Using the Voronoi construction, we find that the distributions of Voronoi volume P(v(V)) and asphericity P(a) appear to be universal properties of dense liquids, supporting the use of packing approaches to understand liquid properties. We also calculate the average free volume along a path of constant density and find that extrapolates to zero at the same temperature T0 that the extrapolated relaxation time diverges. We relate to the Debye-Waller factor, which is measurable by neutron scattering.     

Metal-to-semimetal transition in supercooled liquid silicon

Computer simulations, using the Stillinger-Weber potential, have previously been employed to demonstrate a liquid-liquid transition in supercooled silicon near 1060 K. From calculations of electronic structure using an empirical psuedopotential, we show that silicon undergoes an associated metal to semimetal transition with a resistivity jump of roughly 1 order of magnitude. We show that the electronic states near the Fermi energy become localized in the low temperature phase, and that changes in electronic structure between the two phases arise from a change in atomic structure, and not from a change in density.     

On periodic motions of lattices of Toda type via critical point theory

Communicated by P. Rabinowitz     

Improved sequencing of oxidized cysteine and methionine containing peptides using electron transfer dissociation

Oxidative modifications to the side chains of sulfur-containing amino acids often limit the number of product ions formed during collision-induced dissociation (CID) and thus make it difficult to obtain sequence information for oxidized peptides. In this work, we demonstrate that electron-transfer dissociation (ETD) can be used to improve the sequence information obtained from peptides with oxidized cysteine and methionine residues. In contrast to CID, ETD is found to be much less sensitive to the side-chain chemistry, enabling extensive sequence information to be obtained in cases where CID fails to provide this information. These results indicate that ETD is a valuable technique for studying oxidatively modified peptides and proteins. In addition, we report a unique and very abundant product ion that is formed in the CID spectra of peptides having N-terminal cysteine sulfinic acid residues. The mechanism for this unique dissociation pathway involves a six-membered cyclic intermediate and leads to the facile loss of NH(3) and SO(2), which corresponds to a mass loss of 81 Da. While the facile nature of this dissociation pathway limits the sequence information present in CID spectra of peptides with N-terminal cysteine sulfinic acid residues, extensive sequence information for these peptides can be obtained with ETD.     

Gorenstein dimension of modules over homomorphisms

Given a homomorphism of commutative noetherian rings R→S and an S-module N, it is proved that the Gorenstein flat dimension of N over R, when finite, may be computed locally over S. When, in addition, the homomorphism is local and N is finitely generated over S, the Gorenstein flat dimension equals , where E is the injective hull of the residue field of R. This result is analogous to a theorem of André on flat dimension.     

Hilbert-Samuel functions of modules over Cohen-Macaulay rings

For a finitely generated, non-free module over a CM local ring , it is proved that for the length of is given by a polynomial of degree . The vanishing of is studied, with a view towards answering the question: If there exists a finitely generated -module with such that the projective dimension or the injective dimension of is finite, then is regular? Upper bounds are provided for beyond which the question has an affirmative answer.

     

Characterization and catalytic functionalities of copper oxide catalysts supported on zirconia

A series of zirconia supported copper oxide catalysts with varying copper loadings (1.2-19.1 wt %) were prepared by impregnation method. The catalysts were characterized by X-ray diffraction, UV-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and temperature-programmed desorption of CO2. Copper dispersion and metal area were determined by N2O decomposition method. X-ray diffraction patterns indicate the presence of crystalline CuO phase beyond 2.7 wt % of Cu on zirconia. UV-visible diffuse reflectance spectra suggest the presence of two types of copper species on the ZrO2 support. XPS peaks intensity ratio of Cu 2p3/2 and Zr 3d5/2 was compared with Cu dispersion calculated from N2O decomposition. TPR patterns reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The basicity of the catalysts was found to increase with Cu loading, and the activity of the catalysts was also found to increase with the increase in Cu loading up to 2.7 wt % Cu loading. The catalytic properties were evaluated for the dehydrogenation of cyclohexanol to cyclohexanone and were related to surface properties of the copper species supported on zirconia.     

Dependence of the fragility of a glass former on the softness of interparticle interactions

We study the influence of the softness of the interparticle interactions on the fragility of a glass former by considering three model binary mixture glass formers. The interaction potential between particles is a modified Lennard-Jones type potential, with the repulsive part of the potential varying with an inverse power q of the interparticle distance, and the attractive part varying with an inverse power p. We consider the combinations (12,11) (model I), (12,6) (model II), and (8,5) (model III) for (q,p) such that the interaction potential becomes softer from model I to III. We evaluate the kinetic fragilities from the temperature variation of diffusion coefficients and relaxation times, and a thermodynamic fragility from the temperature variation of the configurational entropy. We find that the kinetic fragility increases with increasing softness of the potential, consistent with previous results for these model systems, but at variance with the thermodynamic fragility, which decreases with increasing softness of the interactions, as well as expectations from earlier results. We rationalize our results by considering the full form of the Adam-Gibbs relation, which requires, in addition to the temperature dependence of the configurational entropy, knowledge of the high temperature activation energies in order to determine fragility. We show that consideration of the scaling of the high temperature activation energy with the liquid density, analyzed in recent studies, provides a partial rationalization of the observed behavior.