General trends in the barriers of catalytic reactions on transition metal surfaces

A catalyst preparation by design is one of the ultimate goals in chemistry. The first step towards this goal is to understand the origin of reaction barriers. In this study, we have investigated several catalytic reactions on some transition metal surfaces, using density functional theory. All the reaction barriers have been determined. By detailed analyses we obtain some insight into the reaction barrier. Each barrier is related to (i) the potential energy surface of reactants on the surface, (ii) the total chemisorption energy of reactants, and (iii) the metal d orbital occupancy and the reactant valency. (C) 2001 American Institute of Physics.

General trends in CO dissociation on transition metal surfaces

Dissociative adsorption is one of the most important reactions in catalysis. In this communication we propose a model aiming to generalize the important factors that affect dissociation reactions. Specifically, for a dissociation reaction, say AB -->A + B, the model connects the dissociation barrier with the association barrier, the chemisorption energies of A and B at the final state and the bonding energy of AB in the gas phase. To apply this model, we have calculated CO dissociation on Ru(0001), Rh(111), Pd(111) (4d transition metals), Os(0001), Ir(111), and Pt(111) (5d transition metals) using density function theory (DFT). All the barriers are determined. We find that the DFT results can be rationalized within the model. The model can also be used to explain many experimental observations. (C) 2001 American Institute of Physics.

Radiotherapy in the presence of contrast agents: a general figure of merit and its application to gold nanoparticles

Delivering sufficient dose to tumours while sparing surrounding tissue is one of the primary challenges of radiotherapy, and in common practice this is typically achieved by using highly penetrating MV photon beams and spatially shaping dose. However, there has been a recent increase in interest in the possibility of using contrast agents with high atomic number to enhance the dose deposited in tumours when used in conjunction with kV x-rays, which see a significant increase in absorption due to the heavy element's high-photoelectric cross-section at such energies. Unfortunately, the introduction of such contrast agents significantly complicates the comparison of different source types for treatment efficacy, as the dose deposited now depends very strongly on the exact composition of the spectrum, making traditional metrics such as beam quality less valuable. To address this, a 'figure of merit' is proposed, which yields a value which enables the direct comparison of different source types for tumours at different depths inside a patient. This figure of merit is evaluated for a 15 MV LINAC source and two 150 kVp sources (both of which make use of a tungsten target, one with conventional aluminium filtration, while the other uses a more aggressive thorium filter) through analytical methods as well as numerical models, considering tissue treated with a realistic concentration and uptake ratio of gold nanoparticle contrast agents (10 mg ml(-1) concentration in 'tumour' volume, 10: 1 uptake ratio). Finally, a test case of human neck phantom is considered with a similar contrast agent to compare the abstract figure to a more realistic treatment situation. Good agreement was found both between the different approaches to calculate the figure of merit, and between the figure of merit and the effectiveness in a more realistic patient scenario. Together, these observations suggest that there is the potential for contrast-enhanced kilovoltage radiation to be a useful therapeutic tool for a number of classes of tumour on dosimetric considerations alone, and they point to the need for further research in this area.

ARTICLE: On the Curious Disappearance of Human Servitude from General International Law

The following study considers the fragmentation of law which occurred in 1956 with regard to the law on servitude. As States were unwilling to go as far as the Universal Declaration on Human in establishing that "no one shall be held in [...] servitude", the negotiators of the 1956 Supplementary Conventions moved to expunge the very term 'servitude' from the text and to replace it with the phrase 'institutions and practices similar to slavery' which could then be abolished 'progressively and as soon as possible'. The negotiation history of the 1956 Convention clear demonstrate that the Universal Declaration on Human was the elephant in the room and that it ultimately lead to a fragmentation of the law as between general international law manifest in the 1956 Supplementary Convention on the one hand and international human rights law on the other. It is for this reason that, for instance the 2001 UN and 2005 Council of Europe trafficking conventions mention both 'practices similar to slavery' and 'servitude' as types of human exploitation to be suppressed in their definition of 'trafficking in persons'.

General local and rectilinear vibrational coordinates consistent with Eckart's conditions

We present a general method to construct a set of local rectilinear vibrational coordinates for a nonlinear molecule whose reference structure does not necessarily correspond to a stationary point of the potential-energy surface. We show both analytically and with a numerical example that the vibrational coordinates satisfy Eckart's conditions. In addition, we find that the Watson Hamiltonian provides a fairly robust description even of highly excited vibrational states of triatomic molecules, except for a few states of large amplitude motion sampling the singular region of the Hamiltonian. These states can be identified through slow convergence.