Luminescence kinetic and association equilibria of lanthanide ions in aqueous solutions. II. Determination of the formation constant of Tb acetato complex by means of luminescence lifetime measurement

The association constant K of mono-acetato complex of Tb³⁺ has been determined at normal p and T conditions by measurement of its luminescence lifetime in aqueous solution containing increasing concentrations of acetate. Two experimental arrangements used for the measurement are described.     

Cluster isobars for high-precision mass spectrometry

Doublet mass measurements of the isobars²⁸Si₃ and¹²C₇ are performed by use of a Penning trap mass spectrometer and the Fourier transform ion cyclotron resonance (FT-ICR). The carbon and silicon cluster ions are produced by laser ablation. Results of these preliminary measurements are presented.     

Acyl- und Alkylidenphosphane. XXVIII. Synthese und Struktur von 1,3-Dibenzyl- und 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetan

Acyl- and Alkylidenephosphines. XXVIII. Synthesis and Structure of 1,3-Dibenzyl- and 1,3-Diethyl-2,4-bis(phenylimino)-1,3-diphosphetane Catalyzed by small amounts of solid sodium hydroxide, the adducts 1a and 1b formed from benzyl- or ethylbis(trimethylsilyl)phosphine and phenylisocyanate, react at +20°C slowly to give hexamethldisiloxane and oligomeric [(phenylimino)methylidene]phosphines. In different solvents the benzyl compound was found to exist only as a mixture of [N,N′-(E)/(Z)]-isomeric 2,4-bis-(phenylimino)-1,3-diphosphetanes 2a with their alkyl groups at the phosphorus atoms in trans position, whereas in case of the ethyl derivative 2b a second pair of [N,N′-(E)/(Z)]-isomeric dimers with their substituents in cis position and two trimeric forms ( 3b and 4b ) could be detected in cyclopentane. [N,N′-(E)]-1r,3t-dibenzyl- ( 2a ) and [N,N′-(E)]-1r,3t-diethyl-2,4-bis(phenylimino)-1,3-diphosphetane 2b isolated from 1,2-dimethoxyethane or cyclopentane, crystallize in the monoclinic space group P2₁/c or P2₁/n, resp., with following dimensions of the unit cell determined at temperatures of measurement of +20 ± 3°C/?130 ± 3°C: a = 2145.4(1)/569.3(1); b = 568.1(2)/719.1(2); c = 1960.2(2)/2042.6(4) pm; β 99.43(1)°/95.03(2)°; Z = (2+2) and 2, resp. X-ray structure determinations (R_w = 0.034/0.041) show both molecules to be centrosymmetric. Characteristic rounded bond lengths (pm) and angles (°) are: endocyclic P? C 185/184; C? P? C 82/81; P? C? P 98/99; exocyclic P? C 186/184; C?N l27/127; C?N? C 121/11.     

VISUAL PIGMENTS—10. SPECTROSCOPY AND PHOTOPHYSICAL DYNAMICS OF RETINOL AND RETINYL ETHER

Abstract— The absorption and emission spectra, lifetimes and quantum yields of all-trans retinol have been examined as a function of solvent and temperature. In addition, the spectroscopy of retinyl ether and 2 other polyene alcohols have been determined. Based on the results obtained, we conclude that the singlet excited state of retinol and retinyl cther is of a forbidden character and of the type loosely called ¹A^-_g. Retinol forms a dimer in an alkane solvent when cooling from 298 to 77 K. A general structure for the dimer is proposed.     

Lifetimes of charged and neutralD mesons

We have measured the lifetimes of hadronically produced charged and neutralD mesons using silicon microstrip detectors and an active silicon target in the NA32 spectrometer at the CERN SPS. We obtainτ _D± = (10.9± _1.5 ^1.9 )·10^?13s andτ _D ^(?)10 = (4.2±0.5)·10^?13s based on 59 and 90 fully reconstructed decays respectively, giving a ratioτ _D±/τ _D ^(?)10 of 2.6 ±0.5.     

Measurements of circular polarization correlations following excitation of Ar and Kr by electron impact

We report measurements of the circular polarization correlation parameterP ₃ for the excitation of the 4s′[1/2] _j=1 state in Ar by 40 eV electrons and for the excitation of the Kr 5s[3/2] _J=1 state by 30 eV electrons at electron scattering angles up to 50°. The measured Ar data are compared to predictions of a distorted wave Born approximation (DWBA). The agreement is in general not very good with theory predictingP ₃ values considerably larger than the measured values in the regime of small scattering angles. In Kr, where the measured data are compared to theoretical predictions from a DWBA, a first-order many-body theory (FOMBT) and a relativistic distorted wave theory (RDW), the level of agreement between experiment and theory is somewhat better. The measuredP ₃ parameters in conjunction with the previously measured linear coherence parametersP ₁ undP ₂ under the same scattering conditions yield the total polarizationP _tot ⁺ which is a measure for the level of coherence in the excitation process. In both cases studied here, we found values of eliminateP _tot ⁺ that were consistent with a fully coherent excitation process.     

Ab Initio High Pressure Investigations of InI

The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s² electron pair in In⁺ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns² electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In⁺ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In⁺ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In⁺ within the zigzag chain, i. e. increasing bonding interactions between the In⁺ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement.