Proton and deuteron position preferences in water clusters: an ab initio study

In order to explore the effect of H-to-D substitution on the zero-point energy (ZPE) of water clusters, Hessians were computed for a database of 53 optimized (H2O)n clusters, 5 < or = n < or = 21, at the B3LYP6-311 + + G** level. The 53 clusters contained 1524 protons, which were sorted into 18 categories according to the type of their donor O and (if not free) acceptor O. Letting deltaZPE[H]* denote the change in ZPE when the proton H* is replaced by D, mean values for deltaZPE[H*] for the H-bonded categories ranged from -2172 cal mol(-1) for H* in a DDAA-DDAA bond to -2118 for H* in a DAA-DDA bond. Mean value for H* free on DAA (respectively, DA) was -2018 (respectively, -1969). For DAA-DDA bonds, and for short H bonds in general, there was a strong inverse correlation between /deltaZPE[H*]/ and the O-H* distance. deltaZPE for multiple H-to-D substitutions was additive, except for a cooperativity effect of -13.7 to -19.7 cal mol(-1) when two substituted protons were in the same H2O unit and a much smaller cooperativity when one proton's donor was the other's acceptor. Implications of these data include a relative preference for D to occupy H bonded rather than free positions in finite water clusters, a value of 3.82 for the disproportionation equilibrium constant of mixed ice at 150 K, increased occupation by H at surface positions of mixed ice, and a larger average coordination number for liquid D2O than for liquid H2O.     

Effects of crystallographic ordering on the magnetic behaviour of (AgIn)1-zMn2zTe2 and (CuIn)1-zMn2zTe2 alloys

Measurements of magnetic susceptibility in the temperature range 4.2–300 K were made on polycrystalline samples of the (AgIn)_{1 - z}Mn_2zTe₂ and (CuIn)_{1 - z}Mn_2zTe₂ alloys, and the data used to give values of spin-glass transition te mperature T_g and Curie-Weiss paramagnetic temperature θ. For any sample for which the X-ray powder photograph indicated an apparently single phase condition, either zinc-blende or chalcopyrite, the susceptibility data could show up to three separate T_g values. These different magnetic conditions are attributed to crystallographic ordering of the Mn ions on the chalcopyrite and zinc-blende lattices, the three observed T_g values corresponding to disordered zinc-blende, ordered zinc-blende and ordered chalcopyrite. The value of θ obtained from the 1/χ vs. T plot is shown to be a weighted mean of the separate values of θ for the phases present. The relative sizes of the T_g peaks and the values of θ for any given sample gives an indication of the amount of each phase present. These amounts were varied by using different methods of heat treatment and it was shown that the magnetic behaviour was consistent with the T(z) phase diagram for the two alloy systems.     

Hydration of soda-lime glass

The hydration of soda-lime glass is studied using resonant nuclear reactions to measure the hydrogen and sodium profiles of hydrated glasses. The rate of growth of the surface layer of hydrated glass is initially proportional to the square root of time as is characteristic of diffusion controlled processes. After longer exposure a steady-state hydration profile is observed, which indicates that in addition to the diffusion controlled reaction there is a slow etching of the glass surface. The measured hydration profiles are discussed in relationship to the Doremus model of interdiffusing ions, which is found to be in good agreement with the data. This model is also discussed in relationship to measured hydration profiles of vacuum heated samples of hydrated glass.     

Adaptive environment classification system for hearing aids

An adaptive sound classification framework is proposed for hearing aid applications. The long-term goal is to develop fully trainable instruments in which both the acoustical environments encountered in daily life and the hearing aid settings preferred by the user in each environmental class could be learned. Two adaptive classifiers are described, one based on minimum distance clustering and one on Bayesian classification. Through unsupervised learning, the adaptive systems allow classes to split or merge based on changes in the ongoing acoustical environments. Performance was evaluated using real-world sounds from a wide range of acoustical environments. The systems were first initialized using two classes, speech and noise, followed by a testing period when a third class, music, was introduced. Both systems were successful in detecting the presence of an additional class and estimating its underlying parameters, reaching a testing accuracy close to the target rates obtained from best-case scenarios derived from non-adaptive supervised versions of the classifiers (about 3% lower performance). The adaptive Bayesian classifier resulted in a 4% higher overall accuracy upon splitting adaptation than the minimum distance classifier. Merging accuracy was found to be the same in the two systems and within 1%-2% of the best-case supervised versions.     

Magnetic susceptibility,transport and Mössbauer measurements in CuFeSe2

The study of the magnetic, transport and Mössbauer properties of eskebornite, CuFeSe₂, shows significant differences from that of its homologous sulfide, chalcopyrite (CuFeS₂). From room temperature down to 77 K, CuFeSe₂ is paramagnetic and metallic with a non-magnetic Mössbauer spectrum showing two equally populated sites for iron with very small quadrupole splitting. It seems clear that the electronic state of iron has evolved in going from chalcopyrite to eskebornite, in which it has a very weak magnetism.     

On the homology of quotients of path algebras

We extend the results and techniques of [Al] to find a method of constructing projective resolutions for certain simple modules over homomorphic images of path algebras. We provide a number of applications in the case when the image algebra is finite dimensional.     

Evidence for the existence of two electronic states in the chalcopyrite-type alloys CuFe(S1−zSez)2

Results of Mössbauer spectroscopy for the chalcopyrite-type of alloys CuFe(S_1–z Se _z )₂ in the range of composition 0z0.45 are presented. Room temperature spectra show two contributions: one is a magnetic spectrum (six lines) with a value of the hyperfine field near to that of chalcopyrite (z=0, in which an antiferromagnetic order occurs belowT=823 K), the other having only one line. The relative area of the single-line contribution increases asz increases. Forz=0.2, we also made Mössbauer measurements as a function of temperature. The ratio of the two contributions evolves according to a Boltzmann law, in which the single line corresponds to the excited state at 81 K above the antiferromagnetic ground state.     

Theoretical prediction of the hydrogen-bond basicity pK(HB)

Ab initio and DFT calculations on around 65 hydrogen bond or Lewis bases and their complexes with hydrogen fluoride have been performed, and a range of calculated properties from both free bases and complexes correlated with pK(HB), an experimental scale of hydrogen-bond basicity. For the entire range of bases, we found that the hydrogen-bond binding Gibbs free energy computed at the B3LYP/6-31+G(d,p) level of theory linearly correlated with pK(HB). Further improvements in the correlation and prediction of pK(HB) were possible with a non-linear fit by considering the hydrogen bonding Gibbs free energy of another possible stereoisomeric 1:1 complex and/or that of a linear 2:1 complex, which included a second hydrogen fluoride.