Nitrogen Molecule Adsorption on Cationic Tantalum Clusters and Rhodium Clusters and Desorption from Their Nitride Clusters Studied by Thermal Desorption Spectrometry.
Adsorption and desorption of N2 molecules onto cationic Ta and Rh clusters in the gas phase were investigated in the temperature range of 300-1000 K by using thermal desorption spectrometry in combination with density functional theory (DFT) calculations. For Ta6(+), the first N2 molecule was found to adsorb dissociatively, and it remained adsorbed when Ta6(+)N2 was heated to 1000 K. In contrast, the second and the subsequent N2 molecules adsorbed weakly as a molecular form and were released into the gas phase when heated to 600 K. The difference can be explained in terms of the activation barrier between the molecular and dissociative forms. On the other hand, when Ta clusters were generated in the presence of N2 gas by the laser ablation of a Ta rod, isomeric clusters, TanNm(+), having heat resistivity were formed. For Rh6(+), N2 adsorbed molecularly at 300 K and desorbed totally at 450 K. These results were consistent with the DFT calculations, indicating that the dissociative adsorption of N2 is endothermic.
The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules.
Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.
Community refinement of glaucoma referrals
AbstractAim To describe a Manchester-based glaucoma referral refinement scheme designed to reduce the number of false-positive referrals to the hospital eye service. To report on the first years results of this scheme and its financial costs to the NHS.Methods Patients with suspected glaucoma, instead of being referred to their GP and then on to the hospital eye service, were referred to a group of specially trained community optometrists working to an agreed set of referral criteria. Those patients who did not meet the referral criteria were returned to the referring optometrist, while those who met the referral criteria were referred directly to Manchester Royal Eye Hospital. The patient's GP was informed in all cases.Results The number of suspect glaucoma cases referred to the Manchester Royal Eye Hospital was reduced by 40%. This figure is close to the percentage of false-positive referrals measured at Manchester Royal Eye Hospital prior to the onset of this study. The information accompanying referral has been improved and the scheme produces a small financial cost saving to the NHS of approximately £17 per patient.Conclusion Community refinement of suspect glaucoma offers some important benefits over the current referral pathway.