Nuclear binding energies and liquid drop parameters in the extended Thomas-Fermi approximation

Using the extended Thomas-Fermi model, we calculate average nuclear binding energies with Skyrme type effective interactions. The total energy is minimized with respect to variations of the nucleon densities without the use of wave functions or adjustable parameters. We obtain binding energies only ～2–7 MeV higher than self consistenly averaged Hartree-Fock energies. By least-square fits we determine the liquid drop parameters of different effective interactions very accurately. Shell effects are added perturbatively and lead to total energies within 5–10 MeV of the exact Hartree-Fock results.     

Spin-orbit splitting in theN-Δ spectra and the deformed baryon model

The absence of appreciable spin-orbit splitting in the low-lying even and odd parity states of the nucleon and delta is puzzling in conventional quark models. A constitutent quark model, in which the quarks interact through gluon as well as pion exchange, and the baryon is allowed to deform in the excited states, may provide a solution to the problem.     

Rotating nuclei in a semiclassical description

A recently proposed semiclassical method for extracting the smoothly varying part of the total energy of an independent particle system is applied to a rotating system. Expressions for the average density distribution, angular momentum, total energy and effective moment of inertia are given.     

The collective response of deformed sodium clusters

We employ the structure-averaged jellium model (SAJM) to obtain the selfconsistent LDA Kohn-Sham ground state of axially deformed sodium clusters with broken leftright symmetry, and calculate the dipole-response of the low-energy isomers using the local RPA (LRPA) scheme in the range 7 < Z ≤ 59. We choose the multipole operators r ^P Y _LM (p=1,...,10; L=1,...,4, M=0,1) as coupled intrinsic modes of the electron system. The collective spectra are compared with recent measurements of the dipole absorption cross section performed by Meibom et al., and we find very good agreement of the positions and strengths of the leading collective modes in the measured range 47 < Z ≤ 59.     

Modified Nilsson model for large sodium clusters

We propose a modified Nilsson model for spheroidal sodium clusters and investigate the modification of shell structure by deformation for sizes up toN=850. For spherical clusters, our potential is fitted to the single-particle spectra obtained from microscopically selfconsistent Kohn-Sham calculations using the jellium model and the local density approximation. Employing Strutinsky's shell-correction method, the surface energy of the jellium model is renormalized to its experimental value. We find good agreement between our theoretically predicted deformed magic numbers and the experimentally observed ones extracted from recent sodium mass abundance spectra.     

Thermal properties of the valence electrons in alkali metal clusters

The finite-temperature density functional approach is applied for the first time to calculate thermal properties of the valence electron system in metal clusters using the spherical jellium model. Both the canonical and the grand canonical formalism are applied and their differences are discussed. We study the temperature dependence of the total free energyF(N) (including a contribution from the ionic jellium background) for spherical neutral clusters containingN atoms. We investigate, in particular, its first and second differences, Δ₁ F =F (N ? 1) ?F (N) and Δ₂ F =F(N + 1) +F(N ? 1) ? 2F(N), and discuss their possible relevance for the understanding of the mass abundance spectra observed in cluster production experiments. We show that the typical enhancement of magic spherical-shell clusters withN=8, 20, 34, 40, 58, 92, 138, 186, 254, 338, 398, 440, 508, 612..., most of which are well established experimentally, is decreasing rather fast with increasing temperatureT and cluster sizeN. We also present electronic entropies and specific heats of spherical neutral clusters. The Koopmans theorem and related approximations for calculating Δ₁ F and Δ₂ F atT > 0 are discussed.     

Non-targeted mercapturic acid screening in urine using LC-MS/MS with matrix effect compensation by postcolumn infusion of internal standard (PCI-IS)

While the targeted analysis of mercapturic acid (MA) metabolites in human urine is used to assess exposure to selected chemicals, this compound class has only rarely been addressed in non-target screening utilizing diagnostic neutral loss liquid chromatography tandem mass spectrometry (LC-MS/MS). Additionally, this type of analysis is severely affected by matrix effects (MEs) causing poor comparability of samples and distortion of signal intensities. However, MEs have been neglected in urinary MA non-target screening so far. Therefore, we developed a non-target screening method relying on neutral loss scanning for MAs using post column infusion of an isotope-labelled standard. For signal correction, we synthesized a structural analogue to MAs, N-acetyl-S-methyl-homocysteine-D₃, lacking the characteristic neutral loss of the MAs. For method development, 16 structurally different model MA compounds and 20 spiked urine samples were used. Twelve out of the 16 model compounds could be analysed by the developed method. We found severe matrix effects (largely signal suppression) for the spiked model compounds, with only 34% of all peaks’ intensities changing by less than a factor of two. This could be compensated by the post column internal standard infusion with now 68% of all peaks’ intensities changing by less than a factor of two. For three compounds, an over-compensation was observed resulting in an increase of signal of up to a factor of 16. In the 20 urine samples, altogether 558 native MAs (between 74 and 175 per sample) could be detected after ME compensation. These results indicate that a large number of so far uncharacterized MAs are present in urine, which yield a potential for biomarker discovery and pattern characterisation.

Graphical Abstract