Some aspects of the dependence of solid-state structure on electron count

The method of moments is used to show how the structures of molecules and solids is sensitive to the number of valence electrons.     

Cumulative subject index volumes 41–45

Orbital correlation diagrams for the black phosphorus to A7 (arsenic) phase transformation for various points in the Brillouin zone are presented and analyzed in symmetry terms. The level doublings observed at the black phosphorus geometry for several points are directly attributable to the nonsymmorphic nature of the space group (Herring's theorem). Doublings observed at the A7 structure derive from the choice of a four-atom, rather than two-atom, unit cell to view the geometrical transformation. The space group requirements at the beginning and end points of the transformation process simply control the form of orbital correlation diagrams. In general, $\text{HOMO}\text{LUMO}$ crossings are found at $\text{k = (}\text{1}\text{2}\text{,α,β)}$ where bonds are made and broken along the x direction, a result with simple analogies to more easily visualized one-dimensional problems.     

An interpretation of structural sorting diagrams for AB type compounds using molecular orbital ideas

The factors governing the structure adopted by a particular AB compound are investigated by deriving two parameters reflecting aspects of the interaction between A and B, using simple molecular orbital ideas, which can be quantified by use of atomic parameters derived from pseudopotential theory. A plot of the values of these two parameters, for a large database of compounds, produces a remarkable topological clustering of AB compounds with the same structure. This structural sorting can also be effected for nonoctet AB compounds if the number of electrons is taken into account. These parameters are related to other indices, R_σ, R_π, previously used by Bloch, Zunger, Phillips et al. to construct structural sorting diagrams. Hence we find a justification for the success of such displays, and shed light on the reasons underpinning structural preference, in terms of the number of valence electrons, and the relative positions of the energy levels of the constituent atoms. There appear to be strong similarities between the electronic reasons behind atomic site preferences in molecules and this site preference or coordination number problem in solids.     

An integrated approach for scheduling health care activities in a hospital

To effectively utilise hospital beds, operating rooms (OR) and other treatment spaces, it is necessary to precisely plan patient admissions and treatments in advance. As patient treatment and recovery times are unequal and uncertain, this is not easy. In response, a sophisticated flexible job-shop scheduling (FJSS) model is introduced, whereby patients, beds, hospital wards and health care activities are respectively treated as jobs, single machines, parallel machines and operations. Our approach is novel because an entire hospital is describable and schedulable in one integrated approach. The scheduling model can be used to recompute timings after deviations, delays, postponements and cancellations. It also includes advanced conditions such as activity and machine setup times, transfer times between activities, blocking limitations and no wait conditions, timing and occupancy restrictions, buffering for robustness, fixed activities and sequences, release times and strict deadlines. To solve the FJSS problem, constructive algorithms and hybrid meta-heuristics have been developed. Our numerical testing shows that the proposed solution techniques are capable of solving problems of real world size. This outcome further highlights the value of the scheduling model and its potential for integration into actual hospital information systems.     

The photophysics of the 2,6 dialkoxy anthracenes: Evidence for excited state side-chain conformational relaxation

Three 2,6 dialkoxyanthracenes with varying ether sidechain lengths (methyl, n-propyl and n-hexyl) are synthesized and characterized. When compared to unsubstituted anthracene, the spectroscopic properties of the alkoxy-anthracenes are significantly different. The oscillator strength appears to be evenly distributed between the L_a and L_b states, rather than concentrated in the low-energy L_a state, and the transition dipole moments are rotated by ～30° in the molecular frame. More importantly, all three derivatives undergo an intramolecular conformational change in the excited state that gives rise to a reshaping of the fluorescence spectrum on the nanosecond timescale. This process has an activation energy of 8±1 kJ/mol. By ～150 K the fluorescence spectrum reflects only the high energy conformer, whose emission lineshape is similar to that of the unsubstituted anthracene. The temperature-dependent changes in the monomeric fluorescence spectra of these compounds will have to be taken into account in future studies of their solid-state spectroscopy.