A stochastic theory of adiabatic invariance

LetI be a set of invariants for a system of differential equations with an ordero() vector field. When order perturbations of zero mean are added to the system we show that, under suitable regularity and ergodicity conditions,I becomes an adiabatic invariant with maximal variations of order one on time scales of order 1/². In the stochastically perturbed case,I behaves asymptotically (for small ) like a diffusion process on 1/² time scales. The results also apply to an interesting class of deterministic perturbations. This study extends the results of Khas'minskii on stochastically averaged systems, as well as some of the deterministic methods of averaging, to such invariants.Supported by NSF grant DMR-8704348     

Ultrafast dynamics of single-walled carbon nanotubes dispersed in polymer films

Wavelength-resolved femtosecond transient absorption spectroscopy is used to follow the electronic dynamics of single-walled carbon nanotubes in polymers following visible photoexcitation. Electron-hole (e-h) pairs give rise to sharp features in the transient spectra that decay in amplitude and exhibit rapid spectral shifts. The decay reflects (e-h) recombination on both short (1.3 ps) and long (35 ps) time scales. Transient spectra also exhibit a broad photobleach at early times that arises from the cooling of a hot electron gas created via excitation at the red edge of a pi-plasmon band.     

Sensing the glass transition in thin and ultrathin polymer films via fluorescence probes and labels

Fluorescence was used to characterize the glass transition in thin and ultrathin supported polymer films with common chromophores. The temperature dependence of the fluorescence intensity exhibits a transition or break upon cooling from the rubbery state to the glassy state, and this is identified as the glass transition. A variety of chromophores are investigated including pyrene, anthracene, and phenanthrene either as dopants, covalently attached to the polymer as a label, or both. The particular choice of the chromophore as well as the nature of the attachment, in the case of labels, have significant impact on the success of this method. Problematic cases include those in which the excited‐state chromophore undergoes significant photochemistry in addition to fluorescence or those in which the particular attachment of the chromophore as a label may allow for conformational interactions that affect the fluorescence quantum yield in a nontrivial way. Polymers that have an intrinsic fluorescence unit, for example, polystyrene, may allow for the fluorescence sensing of the glass transition without added dopants or labels. Finally, it is demonstrated that this technique holds promise for the study of the glass transition in polymer blends and within specific locations in multilayer films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2745–2758, 2002     

Electronic configuration assignment and the importance of low-lying excited states in high-spin imidazole-ligated iron(II) porphyrinates

The synthesis and characterization of six new high-spin deoxymyoglobin models (imidazole(tetraarylporphyrinato)iron(II)) are described. These have been intensively studied by temperature-dependent Mossbauer spectroscopy from 295 to 4.2 K. All complexes show a strong temperature dependence for the quadrupole splitting consistent with low-lying excited states of the same or lower multiplicity. An analysis of the data obtained in applied magnetic fields leads to the assignment of the sign of the quadrupole splitting. All model compounds as well as those of deoxymyoglobin and deoxyhemoglobin, previously studied, have a negative sign for the quadrupole splitting. Although not previously predicted, this experimental observation leads to the assignment of the ground-state electronic configuration for all high-spin imidazole-ligated iron(II) porphyrinates as (d(xz)())(2)(d(yz)())(1)(d(xy)())(1)(d(z)()()2)(1)(d(x)()()2(-)(y)()()2)(1). This is a distinctly different ground-state electronic configuration from other high-spin iron(II) porphyrinates; differences in structural details for the two classes of high-spin complexes are also discussed. The apparent anomaly of differing signs for the zero-field splitting constant between previously studied model complexes and the heme proteins is addressed; the difference appears to result from the fact that the assumptions used in the spin Hamiltonian approach that has been applied to these complexes are not adequately satisfied. Structures of four of the new five-coordinate species have been determined. Core conformations in these derivatives show variation, but these and previously studied compounds reveal a limited number of conformational patterns. The bond lengths and other geometrical parameters such as porphyrin core size and iron out-of-plane displacement support a high-spin state assignment for the iron(II).     

ESCA: A new semi-empirical correlation between core-electron binding energy and valence-electron density

The Siegbahn formula for correlating K-electron chemical shifts with valence-electron density is theoretically derived. A new semi-empirical formula for correlating shifts to 2s- and 2p-orbital populations rather than gross atomic population is proposed and tested.     

Fitness for purpose – the integrating theme of the revised Harmonised Protocol for Proficiency Testing in Analytical Chemistry Laboratories

An overview is presented of the changes in, and rationale of, the 2006 IUPAC Harmonised Protocol for Proficiency Testing in Analytical Chemistry Laboratories. Much experience has accumulated and research has been undertaken since the publication of the first edition of the Harmonised Protocol in 1995. Happily, this experience demonstrated no need for the re-examination of the principles underlying the protocol. However, considerable advances were evident in the way in which the protocol could be put into practice. The most prominent of these advances stems from the increasing awareness of uncertainty as a metrological concept and the corresponding clarification of the idea of fitness for purpose. Fitness for purpose provides a rational basis for converting participants’ results into scores, a basis that provides scores that are fully comparable over many different types of analysis.     

High-K multi-quasiparticle states in No

We report results from an experiment on the decay of the high-K isomers in ²⁵⁴No. We have been able to establish the decay from the known high-lying four-quasiparticle isomer, which we assign as a Kπ=¹⁶⁺${\mathrm{K}}^{\pi }={16}^{+}$ state at an excitation energy of Ex=2.928(3) MeV${\mathrm{E}}_x=2.928(3)\text{MeV}$. The decay of this state passes through a rotational band based on a previously unobserved state at Ex=2.012(2) MeV${\mathrm{E}}_x=2.012(2)\text{MeV}$, which we suggest is based on a two-quasineutron configuration with Kπ=¹⁰⁺${\mathrm{K}}^{\pi }={10}^{+}$. This state in turn decays to a rotational band based on the known Kπ=⁸⁻${\mathrm{K}}^{\pi }=8^{-}$ isomer, which we infer must also have a two quasineutron configuration. We are able to assign many new gamma-rays associated with the decay of the Kπ=⁸⁻${\mathrm{K}}^{\pi }=8^{-}$ isomer, including the identification of a highly K-forbidden ΔK=8$\mathrm{\Delta }\mathrm{K}=8$ E1 transition to the ground-state band. These results provide valuable new information on the orbitals close to the Fermi surface, pairing correlations, deformation and rotational response, and K-conservation in nuclei of the deformed trans-fermium region.     

Proficiency testing in analytical chemistry,microbiology and laboratory medicine – working group discussions on current status,problems and future directions

Working group (WG) discussions on proficiency testing and external quality assessment held at the Eurachem workshop, Portorož, Slovenia 26–27 Sept 2005 are summarised. The discussions focused on performance criteria (WG 1), different aspects of accreditation (WGs 2–3), the revised international harmonised protocol (WG 4), pre- and post-analytical schemes (WG 5), Internet applications (WG 6), experience from the CoEPT project (WG 7), and future aspects (WG 8). Current status, problems and future directions were identified. The WG contained a mix of participants with different expertise. This was done to promote cross-fertilisation of ideas between sectors. The WG issues reflected the content of the keynote lectures and some issues were covered from different perspectives by more than one WG.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia.