Laser spectroscopy of desorbing molecules

In this article the application of tunable dye lasers to desorption phenomena is illuminated. These lasers provide radiation continuously tunable from 105 nm in the vacuum ultraviolet to about 10 m in the mid-IR. By employing either laser induced fluorescence (LIF) or resonance enhanced multiphoton ionization (REMPI) spectroscopy almost all diatomic and many polyatomic molecules can be probed with the sensitivity required to detect desorbing molecules under UHV conditions. The spectral resolution of the lasers is sufficiently high that rotational state selectivity is achieved. Recent developments permit in addition the velocity distributions of molecules to be determined with internal quantum state resolution. Therefore very detailed information about the molecular dynamics has been obtained. In most experiments so far reactive recombinations off surfaces have been investigated. In this paper special emphasis will be given to the recombination of hydrogen on copper and palladium surfaces. For these systems very detailed data about the internal state populations at various surface temperatures have been obtained. The rotational cooling previously observed in molecular beam scattering has also been established for desorption. Strong vibrational excitation has been observed, which in the case of desorption from copper may be associated with the recombination dynamics, whereas for desorption of D₂ from Pd(100) a molecular precursor state might be responsible. By measuring the velocity distribution in each quantum state, the complete energetics of the desorbing molecules has been determined. Some first experiments on laser induced desorption with state selective detection of the desorbing molecules will also be discussed. Finally, making use of the polarization analysis of the signal, alignment effects in the desorption can be observed, permitting observation of molecular dynamics with a magnifying glass.Heisenberg fellow of the Deutsche Forschungsgemeinschaft     

The influence of substrate material and annealing procedure on the properties of superconducting thin films

Thin layers YBa₂Cu₃O_7–x. are deposited by a laser ablation technique using a pulsed excimer laser operating at 308 nm. The influence of the substrate material and the annealing procedure on the superconducting behaviour of the 123 film and the reactions between the film and the substrate are studied by resistance, X-ray patterns and TEM measurements. The best results are obtained for deposition on (100) SrTiO₃ substrates. The resistance of the 1 m thick film shows a metallic behaviour, an onset in superconductivity at a temperature of 90 K, and has zero resistance at 86 K. The 123 material has a preferential oriented c-axis perpendicular to the surface plane.     

The magnetic moment of the 10+ isomer in140Ce andE1 transitions inN=82 isotones caused by outer subshell configurations

Using the reaction¹³⁸Ba(α,2n)¹⁴⁰Ce the magnetic moment of the 10 ₁ ⁺ isomer atE _x =3714.7 keV in theN=82 nucleus¹⁴⁰Ce has been determined by means of the TDPAD method toμ=+10.3(4)μ _N . Measuredg-factors in¹⁴⁰Ce are compared to calculations within the shell model with configuration mixing. For the 10 ₁ ⁺ isomer in¹⁴⁰Ce the four proton configuration π(1g ₇ ^2/2 ,2d ₅ ^2/2 ) has been found to be dominant. From theg-factor measurement strong contributions of multiparticle excitations to thegp2d _3/2,π3s ₁ ² or π1h ₁₁ ² shells and admixtures of neutron excitations to the wave function of the 10 ₁ ⁺ state could be excluded. The strongE1γ-branch of the deexcitation of the 10 ₁ ⁺ isomer in¹⁴⁰Ce can be explained by means of small admixtures of configurations which contain the outer subshell excitationsπ2f _7/2 andπ1h _9/2. On this basisE1 transitions experimentally observed in theN=82 nuclei¹⁴⁰Ce,¹⁴¹Pr and¹⁴⁵Eu may be understood.     

New aspect in transient magnetic fields using heavy ion beams

Transient field precessions have been measured with the first excited 2 ₁ ⁺ -state as probe for ions of²⁸Si traversing Fe at v_ion?1v₀ and 13v₀(v₀=c/137) and⁶²Ni being stopped in Fe. The degree of polarization deduced for the Si ions, p_1s=0.19(6), is consistent with low-velocity data. There is clear evidence that the field strength is attenuated by heavy ion beams. For the⁶²Ni(2 ₁ ⁺ ) state at 1.173 MeV a g-factor value of g=0.34(7) was obtained in good agreement with a previous result.     

Base-atom recognition in protein adsorption to alkyl agaroses.

The three proteins phosphorylase b, calmodulin and fibrinogen are adsorbed onto thioalkyl derivatives of Sepharose much more strongly than onto gels carrying the same alkyl residue coupled via a carbamate linkage. This enhancement of binding onto alkyl-S-Sepharoses compared with alkyl-N-agaroses is not primarily due to an increase in the extent of conformational changes of the proteins occurring on the gel surface. This can be shown in experiments with the tripeptide Trp-Trp-Trp. The Trp tripeptide is also adsorbed with a much higher affinity to butyl-S-Sepharose than to butyl-N-Sepharose, showing that the primary interaction between the immobilized alkyl residue and the amino acids of the protein is decisive for adsorption. A model stressing the strong influence of an atom or a group of atoms at the base of an immobilized alkyl residue is described as "base-atom recognition".     

Simultaneous spectrophotometric determination of Zinc(II) and Nickel(II) with 1-(2-pyridylazo)-2-naphthol

A new procedure for the simultaneous spectrophotometric determination of Zn(II) and Ni(II) with 1-(2-pyridylazo)-2-naphthol as chromogenic reagent has been developed. It is based on resolution of the mixed spectrum over the wavelength range 530–590 nm by applying a least-squares fitting program to standard spectra from each component. The spectra are recorded at an apparent pH of 5.0, provided by an acetate buffer in a mixed 6040 v/v 2-ethoxyethanol/water medium. The relative standard deviations for determination of 13.7 g of Ni and 31.0 g of Zn were 1.9 and 1.0%, respectively (8 replications). The method has been applied to the analysis of iron surfaces coated with a Zn-Ni alloy. The results are compared with those obtained by atomic-absorption spectrophotometry.     

Amperometric flow-injection analysis of hydrazine by electrocatalytic oxidation at cobalt tetraphenylporphyrin modified electrode with heat treatment

Chemically modified electrodes prepared by treating the cobalt tetraphenylporphyrin modified glassy-carbon electrode at 750 degrees (HCME) are shown to catalyze the electrooxidation of hydrazine. The oxidation occurred at +0.63 V vs. Ag/AgCl (saturated potassium chloride) in pH 2.5 media. The catalytic response is evaluated with respect to solution pH, potential scan-rate, concentration dependence and flow-rate. The catalytic stability of the HCME is compared with that of the cobalt tetraphenylporphyrin adsorbed glassy-carbon electrode. The stability of the HCME was excellent in acidic solution and even in solutions containing organic solvent (50% CH(3)OH). When used as the sensing electrode in amperometric detection in flow-injection analysis, the HCME permitted sensitive detection of hydrazine at 0.5 V. The limit of detection was 0.1 ng. The linear range was from 50 ng to 2.4 mug. The method is very sensitive and selective.     

Determination of aqueous ozone for potable water treatment applications by chemiluminescence flow-injection analysis. A feasibility study

The feasibility of determining aqueous ozone by chemiluminescence flow-injection analysis (CL-FIA) was studied for applications in potable water treatment. The ozonated water sample is injected into a pure water carrier and mixed with a dye reagent in front of a photodetector. Many reagents undergo fast CL reactions with aqueous ozone. Most of these reactions display considerable selectivity for ozone over other oxidants of importance in water treatment. Even when there is steady-state response to another oxidant, significant discrimination against the interferents is possible by taking advantage of the much faster kinetics of the CL reaction with ozone. A simple design of a Siemens-type ozone generator and preparation of standard ozone solutions are also described.     

Background levels of uranium in human urine

The literature on the normal content of uranium in urine is reviewed. The reported normal concentration has declined several orders of magnitude over the years, probably due to improvements in analytical technique rather than a real change. The lowest mean values were reported with spectrometry (mean of 23 ng/l in 12 subjects) and thermal ion mass spectrometry (3.4 ng/l in 1 subject). Even spectrometry is not sufficiently sensitive at normal levels, so that techniques such as fission track analysis or mass spectrometry must be used to obtain results above the detection limit of the technique for individual samples.     

Kinetics of chlorine isotope exchange reaction between sodium chloride-36 and triphenyltin chloride in mixed solvents

Isotope exchange reaction between NaCl-36 and triphenyltin chloride in dioxane-water (8020% w/w) and ethanol-water (9010% w/w) mixed solvents has been studied at 25, 35 and 50 °C. The exchange reaction was found to proceed via a bimolecular S_N2, limiting mechanism with reaction rates depending on the solvent used. Inhibition of the exchange in ethanol-water is probably due to solvation of chloride ion through hydrogen bond formation. The rate laws for the exchange reactions are: R_e=3.24×10⁹ e^–65550/RT [Rh₃SnCl] [NaCl] in dioxanewater and R_e=6.61×10⁸ e^–69600/RT [Ph₃SnCl] [NaCl] in ethanol-water, where is the degree of dissociation of NaCl and R_e is the rate of exchange in mol l^–1 s^–1. The activation parameters H^*, S^* and G^* are reported.