Density-functional study of the CO chemisorption on bimetallic Pd–Sn(1 1 0) surfaces

We study the ordered PdSn c(2 × 2), (2 × 1), and PdSn₂ (3 × 1) overlayers deposited on Pd(1 1 0) by using first-principles density-functional calculations. It appears that the two PdSn structures are almost degenerate in the energy. Pd–Sn surfaces we consider do not display the marked buckling with Sn atoms displaced towards vacuum that is common for Pt–Sn surfaces. Low-coverage CO chemisorption at these overlayers and on analogous surface structures on Pd₃Sn is considered. It is shown that inclusion of an empirical correction to the CO adsorption energy changes the stable adsorption site from the long-bridge to the top one in most cases. The adsorption energy decreases with the number of Sn atoms in the vicinity of the adsorption site, and this property correlates well with the position of the centre of gravity of the local Pd d-electron band, and also with the variation of the local density of d-electron states at the Fermi level. The centre-of-gravity value is used to assess the core-level shifts for Pd atoms in various geometries. Most of the calculated data compare rather well with the recent measurements on Pd–Sn overlayers at Pd(1 1 0) as well as with other data on related bimetallic systems.     

Characterization of a near-room-temperature, continuous-wave quantum cascade laser for long-term, unattended monitoring of nitric oxide in the atmosphere

We report on power, spectral linewidth, and mode purity for a cw 5.3 microm quantum cascade laser operated on a thermo-electric cooler. A totally noncryogenic nitric oxide monitor was constructed by integrating this laser with an astigmatic multipass cell and a thermo-electrically cooled infrared detector. The resulting instrument is capable of continuous unattended monitoring of ambient, atmospheric nitric oxide for several weeks with no operator intervention. The detection method was rapid sweep, direct absorption spectroscopy. A detection sensitivity of 0.03 parts in 10(9) is achieved with 30 s averaging time with a path length of 210 m, corresponding to an absorbance path length product of 1.5 x 10(-10) cm(-1).     

On a qualitative approach to the W (001) surface instability and reconstruction

Simple local theory based on the assumption of an important role of Shockley surface states from the vicinity of the Fermi energy in the electron-phonon interaction is used to classify possible reconstructions on the (001) surface of W and Mo. The main conclusion that in-plane deformations (and especially the zig-zag ¯M ₅ one) are more promising than the buckled deformations compares favourably with the results of most of the existing experimental and theoretical investigations.The full (unrevised) version of this paper appeared as a TCM Technical Report (January 15, 1985) from the Cavendish Laboratory, Cambridge University, Cambridge, England, and is available from the first author (M.T.) upon request.     

The photo-dehydro-Diels-Alder (PDDA) reaction

The photo-dehydro-Diels-Alder (PDDA) reaction is a valuable extension of the classical Diels-Alder (DA) reaction. The PDDA reaction differs from the DA reaction by the replacement of one of the C-C-double bonds of the diene moiety by a C-C triple bond and by the photochemical triggering of the reaction. This entails that, in contrast to the DA reaction, the PDDA reaction proceeds according to a multistage mechanism with biradicals and cycloallenes as intermediates. The PDDA reaction provides access to a considerable variety of compound classes. For example, 1-phenylnaphthlenes, 1,1'-binaphthyls, N-heterocyclic biaryls, and naphthalenophanes could be obtained by this reaction.     

Optimal Sobolev Imbeddings Involving Rearrangement-Invariant Quasinorms

Let m and n be positive integers with n2 and 1mn−1. We study rearrangement-invariant quasinorms _R and _D on functions f: (0, 1)→ such that to each bounded domain Ω in ⁿ, with Lebesgue measure |Ω|, there corresponds C=C(|Ω|)>0 for which one has the Sobolev imbedding inequality _R(u*(|Ω| t))C_D(|^mu|* (|Ω| t)), uC^m₀(Ω), involving the nonincreasing rearrangements of u and a certain mth order gradient of u. When m=1 we deal, in fact, with a closely related imbedding inequality of Talenti, in which _D need not be rearrangement-invariant, _R(u*(|Ω| t))C_D((d/dt) ∫_{{x ⁿ : |u(x)|>u*(|Ω| t)}} |(u)(x)| dx), uC¹₀(Ω). In both cases we are especially interested in when the quasinorms are optimal, in the sense that _R cannot be replaced by an essentially larger quasinorm and _D cannot be replaced by an essentially smaller one. Our results yield best possible refinements of such (limiting) Sobolev inequalities as those of Trudinger, Strichartz, Hansson, Brézis, and Wainger.     

Functional properties of rearrangement invariant spaces defined in terms of oscillations

Function spaces whose definition involves the quantity f^**-f^*, which measures the oscillation of f^*, have recently attracted plenty of interest and proved to have many applications in various, quite diverse fields. Primary role is played by the spaces S_p(w), with 0<p<∞ and w a weight function on (0,∞), defined as the set of Lebesgue-measurable functions on R such that f^*(∞)=0 and

     

Determination of DEHP in blood products stored in plastic bags by HPLC

Summary High-performance liquid chromatography (HPLC) was used for the routine monitoring of the plasticizers di(2-ethylhexyl) phthalate (DEHP) and tri(2-ethylhexyl) trimellitate (TOTM), in blood products. It allows easy sample clean-up, solvent extraction using Celite 545 sorbent, good recoveries and opportunity to inject large number of samples without effect on column performance. The plasticizer levels were investigated in two types of poly(vinyl chloride) (PVC) bags containing whole blood plasma, platelet concentrates (PCs) during blood taking and storage.