Low frequency surface resonance modes in electron energy loss spectroscopy

Electron energy loss spectroscopy has proved a powerful probe of vibrational modes of a wide variety of adsorbed species. Here the primary focus has been on modes with frequency well above the maximum phonon frequency of the substrate. Examples are internal vibration modes of adsorbed molecules, possibly shifted significantly in frequency from their gas phase analogues, and high frequency vibrations of an adsorbed molecule or atom against the substrate. Recent experiments explore features in the energy loss spectrum with frequency below the maximum phonon frequency of the substrate, for ordered overlayers of atoms adsorbed on low index metal surfaces. We shall summarize our theoretical studies of such spectra for several adsorbate/substrate combinations, with emphasis oh the physical origin of the features which appear in the calculations. We obtain a good account of the existing data, within the framework of a rather simple lattice dynamical model, and the calculations show that the features which appear are quite sensitive to the symmetry of the adsorption sits, and other details of the surface geometry. We shall illustrate this with several specific examples.     

Surface reconstruction and the Debye-Waller factor

A recently developed soft-mode theory of surface reconstruction¹ is used to calculate the surface Debye-Waller factor (SDWF) as a function of temperature near a supposed transition temperature (T₀) between two reconstruction patterns. The soft surface mode gives rise to a sharp decrease in the SDWF as T₀ is approached, suggesting that an examination the LEED Bragg intensities may help verify the soft mode theory.     

The two-dimensional anharmonic oscillator: The CCC bending mode of C3O2

Newly observed data on the rotational constants of carbon su?ide in excited vibrational states of the low-wavenumber bending vibration ν₇ have been successfully interpreted in terms of the two-dimensional anharmonic oscillator wavefunctions associated with this vibration. By combining these results with published infrared and Raman spectra the vibrational assignment has been extended and a refined bending potential for ν₇ has been derived: this has a minimum at a bending angle of about 24° at the central C atom, with an energy maximum at the linear configuration some 23 cm^?1 above the minimum. From similar data on the combination and hot bands of ν₇ with ν₄ (1587 cm^?1) and ν₂ (786 cm^?1) the effective ν₇ bending potential has also been determined in the one-quantum excited states of ν₄ and ν₂. The effective ν₇ potential shows significant changes from the ground vibrational state; the central hump in the ν₇ potential surface is increased to about 50 cm^?1 in the v₄ = 1 state, and decreased to about 1 cm^?1 in the v₂ = 1 state. In the light of these results vibrational assignments are suggested for most of the observed bands in the infrared and Raman spectra of C₃O₂.     

The Determination of Local Government Electoral Boundaries

For British local government elections, it is necessary to divide the total voting population into sub-groups (wards) such that each sub-group elects one or more representatives. At present there are remarkably few legal requirements governing the way in which this division is done. This study emphasizes the difficulties of formulating the problem of division, puts forward criteria which (hopefully) would look respectable and acceptable if embodied in legislation, and develops a linear programming-plus-heuristics approach which is applied to Bristol County Borough data to enable comparisons with current ward boundaries.     

Ground state of magnetic dimers on metal surfaces

We present model studies of the ground state for magnetic dimers on metal surfaces. We find it can be neither ferromagnetic nor antiferromagnetic, but is often canted for nearest neighbors. Thus, the system cannot be described using bilinear exchange. We give a criterion which can be used quite generally to interrogate the local stability of ferromagnetically or antiferromagnetically aligned dimers, and which also may be used to infer the canting angle when canted states are stable.     

Strongly enhanced hole-phonon coupling in the metallic state of the dilute two-dimensional hole gas

We have studied the temperature dependent phonon emission rate P(T) of a strongly interacting (r(s) > or =22) dilute 2D GaAs hole system using a standard carrier heating technique. In the still poorly understood metallic state, we observe that P(T) changes from P(T) approximately T5 to P(T) approximately T7 above 100 mK, indicating a crossover from screened piezoelectric (PZ) coupling to screened deformation potential (DP) coupling for hole-phonon scattering. Quantitative comparison with theory shows that the long range PZ coupling between holes and phonons has the expected magnitude; however, in the metallic state, the short range DP coupling between holes and phonons is almost 20 times stronger than expected from theory. The density dependence of P(T) shows that it is easier to cool low-density 2D holes in GaAs than higher density 2D hole systems.     

3D ultrasound guided breast biopsy system

Stereotactic X-ray mammography (SM) and ultrasound (US) guidance are commonly used techniques for breast biopsy. While SM provides 3D targeting information and US provides real-time guidance, both techniques have limitations. SM is a long and uncomfortable procedure and the US guided procedure is inherently 2D, requiring a skilled physician for both safety and accuracy. We have developed a 3D US-guided biopsy system to integrate with SM. The dual modality breast biopsy system combines the advantages of both approaches with 3D US and SM targeting, near real-time 3D and real-time 2D US guidance, breast stabilisation and a confined needle trajectory. Our goal is to be able to biopsy a larger percentage of suspicious masses using ultrasound, by clarifying ambiguous structures with mammographic imaging. Using breast phantoms, we have shown that our ultrasound guided biopsy system was capable of targeting artificial lesions that were 3.2 mm in diameter, with a 96% success rate. Through this study, we also demonstrated that our system was equivalent to current clinical practice, for an in vitro biopsy task. Metal beads in known relative positions allowed us to determine the geometry of the SM system, so that stereotactic mammography could be registered to 3D US images. The target registration error was found to be 1.6 mm. This error was dominated by positioning error in the vertical direction (perpendicular to the film surface). As an adjunct to SM, we propose that 3D US could provide more complete imaging information for target identification and real-time monitoring of needle insertion, as well as providing a means for rapid confirmation of biopsy success.     

A definitive synthesis of D-myo-inositol 1,4,5,6-tetrakisphosphate and its enantiomer D-myo-inositol 3,4,5,6-tetrakisphosphate from a novel butane-2,3-diacetal-protected inositol

New and rapid syntheses of the enantiomeric intracellular signalling molecules d-myo-inositol 1,4,5,6-tetrakisphosphate (1 a) and D-myo-inositol 3,4,5,6-tetrakisphosphate (1 b) are described. The synthetic strategy employs the novel butane-2,3-diacetal-protected (BDA-protected) myo-inositol (+/-)-3 ab, directly accessible from myo-inositol on a large scale, and an optical resolution with diastereoisomeric (R)-(-)-acetylmandelate esters. The X-ray crystal structure of (+/-)-4, an unusual side product of acid-catalysed reaction of myo-inositol with butanedione is also presented, and the absolute configurations of 1 a and 1 b are definitively assigned by conversion of key precursors into (+)-bornesitol and L-iditol hexaacetate, respectively. Biological activity of synthetic 1 b was confirmed in comparison with the natural polyphosphate.     

Regioselective synthesis of 3,3‐diethyl‐4‐(methylene)‐1‐quinol‐2‐ones by an intramolecular microwave assisted heck reaction

A protocol for the intramolecular Heck cyclization to afford 3,3‐diethyl‐4‐(methylene)‐1‐quinol‐2‐ones is described. We observed that the use of microwave irradiation increased the efficiency of the reaction. Several examples are presented which show the versatility of the reaction.