Converged properties of clean metal surfaces by all-electron first-principles calculations

All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties.     

Speech deterioration in postlingually deafened adults

Postlinngually deafened adults reading the Rainbow Passage differed from hearing-control subjects in producing greater pitch variability and mean pitch on stressed and unstressed vowels, greater fluctuations in pitch within sentences, less correlation of intrinsic pitch with vowel height and slower temporal parameters. When reading the Phonetic Inventory Sentences, they revealed less differentiation of place of articulation in fricative and plosive consonants. The present findings, taken together with those of longitudinal and implant studies, are applied to constraining models of the role of self hearing in the elaboration of speech.     

Graphical operations on projective spaces

Motivated by the work of Crapo and Rota [6] on the lifting of a projective complex, we introduce a class of invariant operations associated to integral-weighted graphs, which we call graphical operations. Such operations generalize the sixth harmonic of a quadranguler set on a projective line. We determine the expansion of the graphical operations in terms of multi-linear bracket polynomials in a Grassmann-Cayley algebra. Reducibility and compositions of such invariant operations are also investigated with a number of examples.Supported by Courant Instructorship, New York University.     

Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Speech of cochlear implant patients: a longitudinal study of vowel production.

Acoustic parameters were measured for vowels spoken in /hVd/ context by four postlingually deafened recipients of multichannel (Ineraid) cochlear implants. Three of the subjects became totally deaf in adulthood after varying periods of partial hearing loss; the fourth became totally deaf at age four. The subjects received different degrees of perceptual benefit from the prosthesis. Recordings were made before, and at intervals following speech processor activation. The measured parameters included F1, F2, F0, SPL, duration, and amplitude difference between the first two harmonic peaks in the log magnitude spectrum (H 1-H2). Numerous changes in parameter values were observed from pre- to post-implant, with differences among subjects. Many changes, but not all, were in the direction of normative data, and most changes were consistent with hypotheses about relations among the parameters. Some of the changes tended to enhance phonemic contrasts; others had the opposite effect. For three subjects, H 1-H2 changed in a direction consistent with measurements of their average air flow when reading; that relation was more complex for the fourth subject. The results are interpreted with respect to: characteristics of the individual subjects, including vowel identification scores; mechanical interactions among glottal and supraglottal articulations; and hypotheses about the role of auditory feedback in the control of speech production. Almost all the observed differences could be attributed to changes in the average settings of speaking rate, F0 and SPL, which presumably can be perceived without the need for spectral place information. Some observed F2 realignment may be attributable to the reception of spectral cues.     

Effects of short-term auditory deprivation on speech production in adult cochlear implant users.

Speech production parameters of three postlingually deafened adults who use cochlear implants were measured: after 24 h of auditory deprivation (which was achieved by turning the subject's speech processor off); after turning the speech processor back on; and after turning the speech processor off again. The measured parameters included vowel acoustics [F1, F2, F0, sound-pressure level (SPL), duration and H1-H2, the amplitude difference between the first two spectral harmonics, a correlate of breathiness] while reading word lists, and average airflow during the reading of passages. Changes in speech processor state (on-to-off or vice versa) were accompanied by numerous changes in speech production parameters. Many changes were in the direction of normalcy, and most were consistent with long-term speech production changes in the same subjects following activation of the processors of their cochlear implants [Perkell et al., J. Acoust. Soc. Am. 91, 2961-2978 (1992)]. Changes in mean airflow were always accompanied by H1-H2 (breathiness) changes in the same direction, probably due to underlying changes in laryngeal posture. Some parameters (different combinations of SPL, F0, H1-H2 and formants for different subjects) showed very rapid changes when turning the speech processor on or off. Parameter changes were faster and more pronounced, however, when the speech processor was turned on than when it was turned off. The picture that emerges from the present study is consistent with a dual role for auditory feedback in speech production: long-term calibration of articulatory parameters as well as feedback mechanisms with relatively short time constants.     

Surface chemical studies of the influence of In and Al on the decomposition of TEG on GaAs(100)

The interaction of triethylgallium (TEG) with the Ga-stabilized GaAs(100) surface in the presence of In and Al has been investigated using AES (Auger electron spectroscopy), HREELS (high resolution electron energy loss spectroscopy) and TDS (thermal desorption spectroscopy) techniques. Al is shown to greatly increase the saturation surface coverage of TEG on the surface and to suppress the desorption of TEG and diethylgallium (DEG). Etching of the surface Al by TEG is observed, resulting in the formation of gas phase Al organic species. Alkyl migration from GA to Al centres occurs, and the presence of Al substantially enhances the irreversible deposition of C. In is found to enhance DEG desorption and to lower the temperature at which absorbed ethyl groups decompose to gas phase ethene. Computer modelling has been carried out to extract kinetic parameters from measured thermal desorption spectra. These parameters are then used to calculate expected partial growth rates of GaAs during the growth of Ga_xAl_1−xAs and Ga_xIn_1−xAs using TEG. The data provide a molecular level understanding of the GaAs pa rtial growth rate variations arising during the deposition of III–V ternary materials.     

An aqueous route to organically functionalized silica diatom skeletons

Diatomaceous earth was functionalized by grafting organotrialkoxysilane precursors onto the surface of the porous silica cell walls of this biomineral. Vinyl- and mercapto-containing structures were prepared in aqueous media without disruption of the diatomic architecture. Successful grafting of the organic moieties was confirmed using solid state ²⁹Si MAS NMR spectroscopy, and the presence of the intact diatom framework by scanning electron microscopy. The sorption properties of mercaptopropyl-functionalized diatoms towards heavy metals was studied by measuring the accessibility and diffusion rates of mercury(II) species to the binding sites (-SH) by the means of electrochemical methods.     

Ernest Julius Wilczynski (in Memoriam)

Ringrazio il collega dell'Università di Chicago di avermi permesso di pubblicare qui un breve sunto della commemorazione da lui scritta; e sono dolente che lo spazio concessomi non me ne abbia permesso la pubblicazione integrale.Guido Fubini     

Selected-area growth of carbon nanotubes by the combination of focused ion beam and chemical vapor deposition techniques.

In this article, we report a technique for growing carbon nanotubes in a more controllable fashion, which enables us to synthesize nanotubes directly in various forms of designed patterns. This nanofabrication process is based on a combination of focused ion beam (FIB) and chemical vapor deposition (CVD) techniques. In this process, arrays of conductive patterns were first deposited on silicon substrates by directing a gaseous compound (C(9)H(16)Pt) via the capillary needle-sized nozzles within a FIB system. The substrates were then coated with catalyst and further modified by the FIB to localize the position of the catalyst. Finally, the growth of carbon nanotubes on the designed substrates was carried out by CVD of hydrocarbon gases. This fabrication technique has the advantage of positioning carbon nanotubes in selected locations. This may open up opportunities for the direct synthesis of carbon nanotubes onto almost any substrate material, thus allowing fabrication of carbon nanotube-based devices.