Modeling non-harmonic behavior of materials from experimental inelastic neutron scattering and thermal expansion measurements

Based on thermodynamic principles, we derive expressions quantifying the non-harmonic vibrational behavior of materials, which are rigorous yet easily evaluated from experimentally available data for the thermal expansion coefficient and the phonon density of states. These experimentally- derived quantities are valuable to benchmark first-principles theoretical predictions of harmonic and non-harmonic thermal behaviors using perturbation theory, ab initio molecular-dynamics, or Monte-Carlo simulations. We illustrate this analysis by computing the harmonic, dilational, and anharmonic contributions to the entropy, internal energy, and free energy of elemental aluminum and the ordered compound FeSi over a wide range of temperature. Results agree well with previous data in the literature and provide an efficient approach to estimate anharmonic effects in materials.

Parallel implementation of the recurrence method for computing the power-spectral density of thin avalanche photodiodes

A simulation program has been developed to calculate the power-spectral density of thin avalanche photodiodes, which are used in optical networks. The program extends the time-domain analysis of the dead-space multiplication model to compute the autocorrelation function of the APD impulse response. However, the computation requires a large amount of memory space and is very time consuming. We describe our experiences in parallelizing the code using both MPI and OpenMP. Several array partitioning schemes and scheduling policies are implemented and tested Our results show that the OpenMP code is scalable up to 64 processors on an SGI Origin 2000 machine and has small average errors.

Multi-ionization of helium and lithium using the independent electron and independent event models with intrinsic CDW

Cross sections for the multi-ionization of He and Li are presented for impact energies in the range of 50 to 1000 keV/amu. These are calculated using the eikonal initial state approximation to represent the input and exit channels of the active electrons. The ionization process is simulated in a variety of ways, most notably an attempt to account for the effects of electron correlation via the inclusion of a continuum density of states (CDS) term. Inadequacies, of the CDW formulation at small impact parameters, and of the models themselves, are discussed and conclusions are drawn on what repercussions this has for the cross sections calculated.

Vibrational properties of nanometric AB(2) ionic clusters

A broad survey of harmonic dynamics in AB(2) clusters with up to N = 3000 atoms is performed using a simple rigid ion model, with ionic radii selected to give rutile as the ground state structure for the corresponding extended crystal. The vibrational density of states is already close to its bulk counterpart for N similar to 500, with characteristic differences due to surfaces, edges and vertices. Two methods are proposed and tested to map the cluster vibrational states onto the rutile crystal phonons. The net distinction between infrared (IR) active and Raman active modes that exists for bulk rutile becomes more and more blurred as the cluster size is reduced. It is found that, in general, the higher the IR activity of the mode, the more this is affected by the system size. IR active modes are found to spread over a wide frequency range for the finite clusters. Simple models based on either a crude confinement constraint or surface pressure arguments fail to reproduce the results of the calculations. The effects of the stoichiometry and dielectric properties of the surrounding medium on the vibrational properties of the clusters are also investigated.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

The Responses of States to the Comments of the CEDAW Committee on Domestic Violence

This article examines the question of how states have responded to the comments of the United Nations Committee on the Elimination of Discrimination against Women (CEDAW Committee) on the issue of domestic violence, through an analysis of 11 Western European States. It is argued that the majority of the states surveyed are complying with only some of the recommendations of the Committee in relation to domestic violence. This finding serves to highlight the fact that there are certainly major difficulties regarding the implementation of human rights law. This article focuses on the Concluding Observations made by the CEDAW Committee on the reports submitted by the Member States, and problems surrounding these Concluding Observations and the work of the Committee are also examined.

The energy density of jellyfish: Estimates from bomb-calorimetry and proximate-composition

Two techniques are described to calculate energy densities for the bell, gonad and oral arm tissues of three scyphozoan jellyfish (Cyanea capillata, Rhizostoma octopus and Chrysaora hysoscella). First, bomb-calorimetry was used, a technique that is readily available and inexpensive. However, the reliability of this technique for gelatinous material is contentious. Second, further analysis involving the more labour intensive proximate-composition analysis (protein, fat and carbohydrate) was carried out on two species (C capillata and R. octopus). These proximate data were subsequently converted to energy densities. The two techniques (bomb-calorimetry and proximate-composition) gave very similar estimates of energy density. Differences in energy density were found both amongst different species and between different tissues of the same species. Mean ( +/- S.D.) energy density estimates for whole animals from bomb-calorimetry were 0.18 +/- 0.05, 0.11 +/- 0.04, and 0.10 +/- 0.03 kJ g wet mass(-1) for C. capillata, R. octopus, and C. hysoscella respectively. The implications of these low energy densities for species feeding on jellyfish are discussed. (c) 2007 Elsevier B.V. All rights reserved.