Auger transitions in Li-like and Be-like ions

Measurements of the Auger decay of beam-foil excited Be II and Be I levels are reported along with a proposed assignment of the experimental spectra. The Li I, Be II and Be III (1s 2s^2) ^2 S \rightarrow (1s^2 2s)^2 S Auger transitions as presented in this letter represents the first observation of such states in positive ions with Z \le 5.

Observation of two-electron-one-photon transitions in silicon

We report on the observation of K\alpha\alpha X-rays of Si, produced in collisions of 15-28 MeV Si projectiles with various target atoms in the range Z =6 to 29. Energy shifts of X-rays were measured and are compared with theoretical predictions. Cross section ratios for emission of K\alpha\alpha and K\alpha radiation are given.

Transitions between quintet states of doubly excited four-electron ions

Following an earlier observation in F VI we identified the line pair 1s2s2p^2 {^5P}-1s2s2p3d {^5P^0} , {^5D^0} for the elements N, O, Mg, and tentatively for A1 and Si in beam-foil spectra. Assignment was established by comparison with Multi-Configuration Dirac-Fock calculations along the isoelectronic sequence. Using this method we also identified some quartet lines of lithium-like ions with Z > 10.

Molecular computations for reactions and phase transitions: applications to protein stabilization, hydrates and catalysis

In this work we have made significant contributions in three different areas of interest: therapeutic protein stabilization, thermodynamics of natural gas clathrate-hydrates, and zeolite catalysis. In all three fields, using our various computational techniques, we have been able to elucidate phenomena that are difficult or impossible to explain experimentally. More specifically, in mixed solvent systems for proteins we developed a statistical-mechanical method to model the thermodynamic effects of additives in molecular-level detail. It was the first method demonstrated to have truly predictive (no adjustable parameters) capability for real protein systems. We also describe a novel mechanism that slows protein association reactions, called the “gap effect.” We developed a comprehensive picture of methioine oxidation by hydrogen peroxide that allows for accurate prediction of protein oxidation and provides a rationale for developing strategies to control oxidation. The method of solvent accessible area (SAA) was shown not to correlate well with oxidation rates. A new property, averaged two-shell water coordination number (2SWCN) was identified and shown to correlate well with oxidation rates. Reference parameters for the van der Waals Platteeuw model of clathrate-hydrates were found for structure I and structure II. These reference parameters are independent of the potential form (unlike the commonly used parameters) and have been validated by calculating phase behavior and structural transitions for mixed hydrate systems. These calculations are validated with experimental data for both structures and for systems that undergo transitions from one structure to another. This is the first method of calculating hydrate thermodynamics to demonstrate predictive capability for phase equilibria, structural changes, and occupancy in pure and mixed hydrate systems. We have computed a new mechanism for the methanol coupling reaction to form ethanol and water in the zeolite chabazite. The mechanism at 400°C proceeds via stable intermediates of water, methane, and protonated formaldehyde.

Reading hybrid texts : remarks on text/image transitions

The reading of printed materials implies the visual processing of information originated in two distinct semiotic systems. The rapid identification of redundancy, complementation or contradiction rhetoric strategies between the two information types may be crucial for an adequate interpretation of bimodal materials. Hybrid texts (verbal and visual) are particular instances of bimodal materials, where the redundant information is often neglected while the complementary and the contradictory ones are essential.Studies using the 504 ASL eye-tracking system while reading either additive or exhibiting captions (Baptista, 2009) revealed fixations on the verbal material and transitions between the written and the pictorial in a much higher number and duration than the initially foreseen as necessary to read the verbal text. We therefore hypothesized that confirmation strategies of the written information are taking place, by using information available in the other semiotic system.Such eye-gaze patterns obtained from denotative texts and pictures seem to contradict some of the scarce existing data on visual processing of texts and images, namely cartoons (Carroll, Young and Guertain, 1992), descriptive captions (Hegarty, 1992 a and b), and advertising images with descriptive and explanatory texts (cf. Rayner and Rotello, 2001, who refer to a previous reading of the whole text before looking at the image, or even Rayner, Miller and Rotello, 2008 who refer to an earlier and longer look at the picture) and seem to consolidate findings of Radach et al. (2003) on systematic transitions between text and image.By framing interest areas in the printed pictorial material of non redundant hybrid texts, we have identified the specific areas where transitions take place after fixations in the verbal text. The way those transitions are processed brings a new interest to further research.

Sudden stratospheric warmings as noise-induced transitions

Sudden stratospheric warmings (SSWs) are usually considered to be initiated by planetary wave activity. Here it is asked whether small-scale variability (e.g., related to gravity waves) can lead to SSWs given a certain amount of planetary wave activity that is by itself not sufficient to cause a SSW. A highly vertically truncated version of the Holton–Mass model of stratospheric wave–mean flow interaction, recently proposed by Ruzmaikin et al., is extended to include stochastic forcing. In the deterministic setting, this low-order model exhibits multiple stable equilibria corresponding to the undisturbed vortex and SSW state, respectively. Momentum forcing due to quasi-random gravity wave activity is introduced as an additive noise term in the zonal momentum equation. Two distinct approaches are pursued to study the stochastic system. First, the system, initialized at the undisturbed state, is numerically integrated many times to derive statistics of first passage times of the system undergoing a transition to the SSW state. Second, the Fokker–Planck equation corresponding to the stochastic system is solved numerically to derive the stationary probability density function of the system. Both approaches show that even small to moderate strengths of the stochastic gravity wave forcing can be sufficient to cause a SSW for cases for which the deterministic system would not have predicted a SSW.

Poverty, migration and sex work: youth transitions in Ethiopia

Despite an emerging body of work on youth transitions, research has yet to explore the often unconventional routes to adulthood for young people marginalised through poverty. By drawing on interviews with 60 young commercial sex workers in Ethiopia, this paper explores the connections between poverty, migration and sex work and demonstrates that sex work provides a risky alternative, but often successful, path to independence for some rural-urban migrants. The paper concludes by offering recommendations for policies that seek to support young sex workers by enabling them to maintain their independence while seeking different employment.

Poverty, migration and sex work: youth transitions in Ethiopia

Despite an emerging body of work on youth transitions, research has yet to explore the often unconventional routes to adulthood for young people marginalised through poverty. By drawing on interviews with 60 young commercial sex workers in Ethiopia, this paper explores the connections between poverty, migration and sex work and demonstrates that sex work provides a risky alternative, but often successful, path to independence for some rural-urban migrants. The paper concludes by offering recommendations for policies that seek to support young sex workers by enabling them to maintain their independence while seeking different employment.

‘We are managing our own lives...’: life transitions and care in sibling-headed households affected by AIDS in Tanzania and Uganda

This paper explores the ways that young people express their agency and negotiate complex lifecourse transitions according to gender, age and inter- and intra-generational norms in sibling-headed households affected by AIDS in East Africa. Based on findings from a qualitative and participatory pilot study in Tanzania and Uganda, I examine young people's socio-spatial and temporal experiences of heading the household and caring for their siblings following their parent's/relative's death. Key dimensions of young people's caring pathways and life transitions are discussed: transitions into sibling care; the ways young people manage changing roles within the family; and the ways that young people are positioned and seek to position themselves within the community. The research reveals the relational and embodied nature of young people's life transitions over time and space. By living together independently, young people constantly reproduce and reconfigure gendered, inter- and intra-generational norms of ‘the family’, transgressing the boundaries of ‘childhood’, ‘youth’ and ‘adulthood’. Although young people take on ‘adult’ responsibilities and demonstrate their competencies in ‘managing their own lives’, this does not necessarily translate into more equal power relations with adults in the community. The research reveals the marginal ‘in-between’ place that young people occupy between local and global discourses of ‘childhood’ and ‘youth’ that construct them as ‘deviant’. Although young people adopt a range of strategies to resist marginalisation and harassment, I argue that constraints of poverty, unequal gender and generational power relations and the emotional impacts of sibling care, stigmatisation and exclusion can undermine their ability to exert agency and control over their sexual relationships, schooling, livelihood strategies and future lifecourse transitions.

Selection rules for rovibronic transitions in symmetric top molecules

A simple diagrammatic rule is presented for determining the rotational selection rules governing transitions between any pair of vibronic states in electric dipole spectra of symmetric top molecules. The rule is useful in cases where degenerate vibronic levels with first-order Coriolis splittings occur, because it gives immediately the selection rule for the (+l) and (-l) components in any degenerate state. The rule is also helpful in determining the symmetry species and the effective zeta constants in overtone and combination levels involving degenerate vibrations. Particular attention is devoted to the conventions concerning the signs of zeta constants.

Raman selection rules for vibration-rotation transitions in symmetric top molecules

Symmetry restrictions on Raman selection rules can be obtained, quite generally, by considering a Raman allowed transition as the result of two successive dipole allowed transitions, and imposing the usual symmetry restrictions on the dipole transitions. This leads to the same results as the more familiar polarizability theory, but the vibration-rotation selection rules are easier to obtain by this argument. The selection rules for symmetric top molecules involving the (+l) and (-l) components of a degenerate vibrational level with first-order Coriolis splitting are derived in this paper. It is shown that these selection rules depend on the order of the highest-fold symmetry axis Cn, being different for molecules with n=3, n=4, or n ≧ 5; moreover the selection rules are different again for molecules belonging to the point groups Dnd with n even, and Sm with 1/2m even, for which the highest-fold symmetry axes Cn and Sm are related by m=2n. Finally it is shown that an apparent anomaly between the observed Raman and infra-red vibration-rotation spectra of the allene molecule is resolved when the correct selection rules are used, and a value for the A rotational constant of allene is derived without making use of the zeta sum rule.

Argon predissociation spectroscopy of the OH-center dot H2O and Cl-center dot H2O complexes in the 1000-1900 cm(-1) region: Intramolecular bending transitions and the search for the shared-proton fundamental in the hydroxide monohydrate

We present argon predissociation vibrational spectra of the OH-.H2O and Cl-.H2O complexes in the 1000-1900 cm(-1) energy range, far below the OH stretching region reported in previous studies. This extension allows us to explore the fundamental transitions of the intramolecular bending vibrations associated with the water molecule, as well as that of the shared proton inferred from previous assignments of overtones in the higher energy region. Although the water bending fundamental in the Cl-.H2O spectrum is in very good agreement with expectations, the OH-.H2O spectrum is quite different than anticipated, being dominated by a strong feature at 1090 cm(-1). New full-diniensionality calculations of the OH-.H2O vibrational level structure using diffusion Monte Carlo and the VSCF/CI methods indicate this band arises from excitation of the shared proton.

Pressure-jump X-ray studies of liquid crystal transitions in lipids

In this paper, we give an overview of our studies by static and time-resolved X-ray diffraction of inverse cubic phases and phase transitions in lipids. In 1, we briefly discuss the lyotropic phase behaviour of lipids, focusing attention on non-lamellar structures, and their geometric/topological relationship to fusion processes in lipid membranes. Possible pathways for transitions between different cubic phases are also outlined. In 2, we discuss the effects of hydrostatic pressure on lipid membranes and lipid phase transitions, and describe how the parameters required to predict the pressure dependence of lipid phase transition temperatures can be conveniently measured. We review some earlier results of inverse bicontinuous cubic phases from our laboratory, showing effects such as pressure-induced formation and swelling. In 3, we describe the technique of pressure-jump synchrotron X-ray diffraction. We present results that have been obtained from the lipid system 1:2 dilauroylphosphatidylcholine/lauric acid for cubic-inverse hexagonal, cubic-cubic and lamellar-cubic transitions. The rate of transition was found to increase with the amplitude of the pressure-jump and with increasing temperature. Evidence for intermediate structures occurring transiently during the transitions was also obtained. In 4, we describe an IDL-based 'AXCESS' software package being developed in our laboratory to permit batch processing and analysis of the large X-ray datasets produced by pressure-jump synchrotron experiments. In 5, we present some recent results on the fluid lamellar-Pn3m cubic phase transition of the single-chain lipid 1-monoelaidin, which we have studied both by pressure-jump and temperature-jump X-ray diffraction. Finally, in 6, we give a few indicators of future directions of this research. We anticipate that the most useful technical advance will be the development of pressure-jump apparatus on the microsecond time-scale, which will involve the use of a stack of piezoelectric pressure actuators. The pressure-jump technique is not restricted to lipid phase transitions, but can be used to study a wide range of soft matter transitions, ranging from protein unfolding and DNA unwinding and transitions, to phase transitions in thermotropic liquid crystals, surfactants and block copolymers.