Density functional and Monte Carlo studies of sulfur. II. Equilibrium polymerization of the liquid phase

The equilibrium polymerization of sulfur is investigated by Monte Carlo simulations. The potential energy model is based on density functional results for the cohesive energy, structural, and vibrational properties as well as reactivity of sulfur rings and chains [Part I, J. Chem. Phys. 118, 9257 (2003)]. Liquid samples of 2048 atoms are simulated at temperatures 450less than or equal toTless than or equal to850 K and P=0 starting from monodisperse S-8 molecular compositions. Thermally activated bond breaking processes lead to an equilibrium population of unsaturated atoms that can change the local pattern of covalent bonds and allow the system to approach equilibrium. The concentration of unsaturated atoms and the kinetics of bond interchanges is determined by the energy DeltaE(b) required to break a covalent bond. Equilibrium with respect to the bond distribution is achieved for 15less than or equal toDeltaE(b)less than or equal to21 kcal/mol over a wide temperature range (Tgreater than or equal to450 K), within which polymerization occurs readily, with entropy from the bond distribution overcompensating the increase in enthalpy. There is a maximum in the polymerized fraction at temperature T-max that depends on DeltaE(b). This fraction decreases at higher temperature because broken bonds and short chains proliferate and, for Tless than or equal toT(max), because entropy is less important than enthalpy. The molecular size distribution is described well by a Zimm-Schulz function, plus an isolated peak for S-8. Large molecules are almost exclusively open chains. Rings tend to have fewer than 24 atoms, and only S-8 is present in significant concentrations at all T. The T dependence of the density and the dependence of polymerization fraction and degree on DeltaE(b) give estimates of the polymerization temperature T-f=450+/-20 K. (C) 2003 American Institute of Physics.

Light emission from scanning tunnelling microscope on polycrystalline Au films - what is happening at the single-grain level?

When operated with a metallic tip and sample the scanning tunnelling microscope constitutes a nanoscale, plasmonic light source yielding broadband emission up to a photon energy determined by the applied bias. The emission is due to tunnelling electron excitation and subsequent radiative decay of localized plasmon modes, which can be on the lateral scale of a single metal grain (similar to 25 nm) or less. For a Au-tip/Au-polycrystalline sample under ambient conditions it is found that the intensity and spectral content of the emitted light are not dependent on the lateral grain dimension, but are predominantly determined by the tip geometry. However, the intensity increases strongly with increasing film thickness (grain depth) up to 20-25 nm or approximately the skin depth of the Au film. Photon maps can show less emissive grains and two classes of this occurrence are distinguished. The first is geometrical in origin - a double-tip structure in this case - while the second is due to a contamination-induced lowering of the local work function that causes the tunnel gap to increase. It is suggested that differences in work-function lowering between grains presenting different crystalline facets, combined with an exponential decay in emitted light intensity with tip - sample distance, leads to grain contrast. These results are relevant to tip-enhanced Raman scattering and the fabrication of micro/nano-scale planar, light-emitting tunnel devices.

Finite temperature dense matter studies on next-generation light sources

The construction of short-pulse tunable soft x-ray free electron laser sources based on the self-amplified spontaneous emission process will provide a major advance in capability for dense plasma-related and warm dense matter (WDM) research. The sources will provide 10(13) photons in a 200-fs duration pulse that is tunable from approximately 6 to 100 nm. Here we discuss only two of the many applications made possible for WDM that has been severely hampered by the fact that laser-based methods have been unavailable because visible light will not propagate at electron densities of n(e) greater than or equal to 10(22) cm(-3). The next-generation light sources will remove these restrictions.

Electron-impact ionization of hydrogen-like iron ions

Electron-impact ionization cross sections have been determined for hydrogen like iron ions at selected electron energies between 1.45 and 4.3 times the threshold energy. The cross sections were obtained by measuring the equilibrium ionization balance in an electron beam ion trap. This ionization balance is obtained from x-ray measurements of radiative recombination into the K-shell of hydrogen-like and bare iron ions. The measured cross sections are compared with distorted-wave calculations and several semiempirical formulations.

Dielectronic recombination of He-like to C-like iodine ions

KLL dielectronic recombination resonances, where a free electron is captured into the L shell and at the same time a K shell electron is excited into the L shell, have been measured for open shell iodine ions by measuring the detected yield of escaping ions of various charge states and modeling the charge balance in an electron beam ion trap. In the modeling, the escape from the trap and multiple charge exchange were considered. Extracted ions were used to measure the charge balance in the trap. The different charge states were clearly separated, which along with the correction for artifacts connected with ion escape and multiple charge exchange made the open shell highly charged ion measurements of this type possible for the first time. From the measured spectra resonant strengths were obtained. The results were 4.27(39)x10(-19) cm(2) eV, 2.91(26)x10(-19) cm(2) eV, 2.39(22)x10(-19) cm(2) eV, 1.49(14)x10(-19) cm(2) eV and 7.64(76)x10(-20) cm(2) eV for the iodine ions from He-like to C-like, respectively.

Attachment Style in Adults who Failed to Thrive as Children: Outcomes of a 20 Year Follow-up Study of Factors Influencing Maintenance or Change in Attachment Style

A group of children identified as non-organic failure-to-thrive between 1977 and 1980 were investigated, assessed and provided with social work intervention and treatment. Those children and their families have been followed up for the last 20 years. The current paper examines the stability of an internal working model in a sample of individuals who had failed to thrive as children, by comparing each individual's adult attachment style with their childhood attachment to their mother. In this sample, several cases showed changes from insecure to secure attachment styles. Possible reasons are discussed for positive and negative changes, as well as cases when there was no change in attachment style. These include the effectiveness of intervention in addition to changes in life circumstances. The findings suggest that when appropriate support and intervention is provided, or when different circumstances or relationships are experienced, internal working models can change.

R-matrix theory of electron molecule scattering

This paper presents an overview of R-matrix theory of electron scattering by diatomic and polyatomic molecules. The paper commences with a detailed discussion of the fixed-nuclei approximation which in recent years has been used as the basis of the most accurate ab initio calculations. This discussion includes an overview of the computer codes which enable electron collisions with both diatomic and polyatomic molecules to be calculated. Nuclear motion including rotational and vibrational excitation and dissociation is then discussed. In non-resonant energy regions, or when the scattered electron energy is not close to thresholds, the adiabatic-nuclei approximation can be successfully used. However, when these conditions are not applicable, non-adiabatic R-matrix theory must be used and a detailed discussion of this theory is given. Finally, recent applications of the theory to treat electron scattering by polyatomic molecules are reviewed and a detailed comparison of R-matrix calculations and experimental measurements for water is presented.

Mapping the evolution of optically generated rotational wave packets in a room-temperature ensemble of D2

A coherent superposition of rotational states in D2 has been excited by nonresonant, ultrafast (12 fs), intense (2×1014 W cm-2) 800 nm laser pulses, leading to impulsive dynamic alignment. Field-free evolution of this rotational wave packet has been mapped to high temporal resolution by a time-delayed pulse, initiating rapid double ionization, which is highly sensitive to the angle of orientation of the molecular axis with respect to the polarization direction, . The detailed fractional revivals of the neutral D2 wave packet as a function of and evolution time have been observed and modeled theoretically.

Operation of a free-electron laser from the extreme ultraviolet to the water window

We report results on the performance of a free-electron laser operating at a wavelength of 13.7 nm where unprecedented peak and average powers for a coherent extreme-ultraviolet radiation source have been measured. In the saturation regime, the peak energy approached 170 J for individual pulses, and the average energy per pulse reached 70 J. The pulse duration was in the region of 10 fs, and peak powers of 10 GW were achieved. At a pulse repetition frequency of 700 pulses per second, the average extreme-ultraviolet power reached 20 mW. The output beam also contained a significant contribution from odd harmonics of approximately 0.6% and 0.03% for the 3rd (4.6 nm) and the 5th (2.75 nm) harmonics, respectively. At 2.75 nm the 5th harmonic of the radiation reaches deep into the water window, a wavelength range that is crucially important for the investigation of biological samples.

An efficient method of radiation attenuation through aircraft cooling vents

Some critical avionic systems require cooling air via vents on the side of the aircraft, thus creating leakage points for high-intensity electromagnetic radiation. This paper presents a novel application of high-intensity radiated field (HIRF) shielding using a rectangular waveguide array, while maintaining cooling airflow requirements. Signal attenuation versus frequency and depth of the array has been calculated using closed-form equations. The simulation and measurement results are in good agreement with the calculated values. (C) 2004 Wiley Periodicals, Inc.