5,152 research outputs found
Towards modular compilers for effects
Compilers are traditionally factorised into a number of separate phases, such as parsing, type checking, code generation, etc. However, there is another potential factorisation that has received comparatively little attention: the treatment of separate language features, such as mutable state, input/output, exceptions, concurrency and so forth. In this article we focus on the problem of modular compilation, in which the aim is to develop compilers for separate language features independently, which can then be combined as required. We summarise our progress to date, issues that have arisen, and further wor
Accurate effective pair potentials for polymer solutions
Dilute or semi-dilute solutions of non-intersecting self-avoiding walk (SAW)
polymer chains are mapped onto a fluid of ``soft'' particles interacting via an
effective pair potential between their centers of mass. This mapping is
achieved by inverting the pair distribution function of the centers of mass of
the original polymer chains, using integral equation techniques from the theory
of simple fluids. The resulting effective pair potential is finite at all
distances, has a range of the order of the radius of gyration, and turns out to
be only moderately concentration-dependent. The dependence of the effective
potential on polymer length is analyzed in an effort to extract the scaling
limit. The effective potential is used to derive the osmotic equation of state,
which is compared to simulation data for the full SAW segment model, and to the
predictions of renormalization group calculations. A similar inversion
procedure is used to derive an effective wall-polymer potential from the center
of mass density profiles near the wall, obtained from simulations of the full
polymer segment model. The resulting wall-polymer potential turns out to depend
strongly on bulk polymer concentration when polymer-polymer correlations are
taken into account, leading to a considerable enhancement of the effective
repulsion with increasing concentration. The effective polymer-polymer and
wall-polymer potentials are combined to calculate the depletion interaction
induced by SAW polymers between two walls. The calculated depletion interaction
agrees well with the ``exact'' results from much more computer-intensive direct
simulation of the full polymer-segment model, and clearly illustrates the
inadequacy -- in the semi-dilute regime -- of the standard Asakura-Oosawa
approximation based on the assumption of non-interacting polymer coils.Comment: 18 pages, 24 figures, ReVTeX, submitted to J. Chem. Phy
Unusual Photophysical Properties of Porphyrin-Based Supramolecular Polymers Unveiled: The Role of Metal Ligands and Side Group Amide Connectivity
Supramolecular polymers based on porphyrins are an interesting model system, since the self-assembly and thus the photophysics can be modified by the chemical structure of the porphyrins, e.g., by a metal inserted in the ligand or by different (solubilizing) side groups. Here, we investigate the photophysical properties of supramolecular polymers based on free-base and Zn-centered porphyrins, each with different amide connectivity in the side chains, by absorption and (time-resolved) photoluminescence spectroscopy on solutions. We find that for all porphyrin derivatives the B-band absorption of supramolecular polymers is a superposition of H- and J-type aggregate spectra, while the Q-band absorption indicates only J-type aggregation. The emission of supramolecular polymers stems exclusively from the Q-band and shows only J-type behavior. For supramolecular polymers based on the free-base porphyrins, we identify only a single aggregate species, whereas for Zn-centered porphyrins, two distinct species coexist in solution, each with a (slightly) different arrangement of monomers. We rationalize this complex behavior by a slip-stacking of porphyrins along the direction of one of the two B-band transition dipole moments, resulting in simultaneous H- and J-type intermolecular coupling in the B-band. In the Q-band, with its transition dipole moments oriented 45° relative to the corresponding B-band moments, only J-type coupling is thus present. Our results demonstrate that the self-assembly and the photophysics of supramolecular polymers based on porphyrins can only be fully understood if spectral information from all bands is considered
Unusual Photophysical Properties of Porphyrin-Based Supramolecular Polymers Unveiled: The Role of Metal Ligands and Side Group Amide Connectivity
Supramolecular polymers based on porphyrins are an interesting model system, since the self-assembly and thus the photophysics can be modified by the chemical structure of the porphyrins, e.g., by a metal inserted in the ligand or by different (solubilizing) side groups. Here, we investigate the photophysical properties of supramolecular polymers based on free-base and Zn-centered porphyrins, each with different amide connectivity in the side chains, by absorption and (time-resolved) photoluminescence spectroscopy on solutions. We find that for all porphyrin derivatives the B-band absorption of supramolecular polymers is a superposition of H- and J-type aggregate spectra, while the Q-band absorption indicates only J-type aggregation. The emission of supramolecular polymers stems exclusively from the Q-band and shows only J-type behavior. For supramolecular polymers based on the free-base porphyrins, we identify only a single aggregate species, whereas for Zn-centered porphyrins, two distinct species coexist in solution, each with a (slightly) different arrangement of monomers. We rationalize this complex behavior by a slip-stacking of porphyrins along the direction of one of the two B-band transition dipole moments, resulting in simultaneous H- and J-type intermolecular coupling in the B-band. In the Q-band, with its transition dipole moments oriented 45° relative to the corresponding B-band moments, only J-type coupling is thus present. Our results demonstrate that the self-assembly and the photophysics of supramolecular polymers based on porphyrins can only be fully understood if spectral information from all bands is considered
Mesoscopic order and the dimentionality of long-range resonance energy transfer in supramolecular semiconductors
We present time-resolved photoluminescence measurements on two series of
oligo-p-phenylenevinylene materials that self-assemble into supramolecular
nanostructures with thermotropic reversibility in dodecane. One set of
derivatives form chiral, helical stacks while the second set form less
organised, frustrated stacks. Here we study the effects of supramolecular
organisation on the resonance energy transfer rates. We measure these rates in
nanoassemblies formed with mixed blends of oligomers and compare them with the
rates predicted by Foerster theory. Our results and analysis show that control
of supramolecular order in the nanometre lengthscale has a dominant effect on
the efficiency and dimentionality of resonance energy transfer.Comment: 17 Pages, 5 Figures, Submitted to J. Chem. Phy
Imaging-documented repeated intratumoral hemorrhage in vestibular schwannoma: a case report
Intratumoral hemorrhage in vestibular schwannomas is rare. Symptoms often have an acute onset and include headache, nausea, vomiting, vertigo, and depressed consciousness. Intratumoral hemorrhage is probably caused by vascular fragility associated with tumor characteristics and growth. With hemorrhage in VS being rare, repeated hemorrhage has only been reported twice, and on clinical grounds only. The present report details the case of acute neurological deterioration in a patient with repeated intratumoral hemorrhage inside a vestibular schwannoma with computed tomography and magnetic resonance imaging confirmation. To our knowledge, repeated hemorrhage in vestibular schwannoma with radiological confirmation has not been reported before
Collisional and thermal ionization of sodium Rydberg atoms I. Experiment for nS and nD atoms with n=8-20
Collisional and thermal ionization of sodium nS and nD Rydberg atoms with
n=8-20 has been studied. The experiments were performed using a two-step pulsed
laser excitation in an effusive atomic beam at atom density of about 2 10^{10}
cm^{-3}. Molecular and atomic ions from associative, Penning, and thermal
ionization processes were detected. It has been found that the atomic ions were
created mainly due to photoionization of Rydberg atoms by photons of blackbody
radiation at the ambient temperature of 300K. Blackbody ionization rates and
effective lifetimes of Rydberg states of interest were determined. The
molecular ions were found to be from associative ionization in Na(nL)+Na(3S)
collisions. Rate constants of associative ionization have been measured using
an original method based on relative measurements of Na_{2}^{+} and Na^{+} ion
signals.Comment: 23 pages, 10 figure
Optical properties of an ensemble of G-centers in silicon
We addressed the carrier dynamics in so-called G-centers in silicon
(consisting of substitutional-interstitial carbon pairs interacting with
interstitial silicons) obtained via ion implantation into a
silicon-on-insulator wafer. For this point defect in silicon emitting in the
telecommunication wavelength range, we unravel the recombination dynamics by
time-resolved photoluminescence spectroscopy. More specifically, we performed
detailed photoluminescence experiments as a function of excitation energy,
incident power, irradiation fluence and temperature in order to study the
impact of radiative and non-radiative recombination channels on the spectrum,
yield and lifetime of G-centers. The sharp line emitting at 969 meV (1280
nm) and the broad asymmetric sideband developing at lower energy share the same
recombination dynamics as shown by time-resolved experiments performed
selectively on each spectral component. This feature accounts for the common
origin of the two emission bands which are unambiguously attributed to the
zero-phonon line and to the corresponding phonon sideband. In the framework of
the Huang-Rhys theory with non-perturbative calculations, we reach an
estimation of 1.60.1 \angstrom for the spatial extension of the
electronic wave function in the G-center. The radiative recombination time
measured at low temperature lies in the 6 ns-range. The estimation of both
radiative and non-radiative recombination rates as a function of temperature
further demonstrate a constant radiative lifetime. Finally, although G-centers
are shallow levels in silicon, we find a value of the Debye-Waller factor
comparable to deep levels in wide-bandgap materials. Our results point out the
potential of G-centers as a solid-state light source to be integrated into
opto-electronic devices within a common silicon platform
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