Dendritic polyelectrolytes revisited through the Poisson-Boltzmann-Flory theory and the Debye-Hückel approximation.

The properties of a dendritic polyelectrolyte in equilibrium with a reservoir of monovalent salts are investigated using the cell model and the Poisson-Boltzmann-Flory theory. Within this approach we use the Debye-Hückel approximation to solve the Poisson-Boltzmann equation and minimize the semi-grand potential of the system with respect to the size of the molecule which enables us to inspect its conformations as well as the electric field, the ionic density profile, the overall charge density, the effective charge of the dendrimer and the osmotic pressure based on their response to the salt concentration and the dendrimer charge. The model predicts pronounced trapping of salt ions, a local charge neutrality and a zero electric field in the volume of the molecule as well as oscillations of the density profiles and the electric field in the vicinity of the dendrimer-bulk interface. As a result of ion trapping and screening of Coulomb interactions monovalent salts are found to have a minor effect on the size of the dendrimer. Specifically, the dendrimer exists in slightly swollen states as compared to the neutral molecule which indicates that the conformational properties of the polyelectrolyte depend weakly on monovalent salts. These observations harmonise with the equilibrium behavior of the dendrimer pressure, the internal pressure and the bulk pressure, respectively.

Dendritic polyelectrolytes as seen by the Poisson-Boltzmann-Flory theory.

G3-G9 dendritic polyelectrolytes accompanied by counterions are investigated using the Poisson-Boltzmann-Flory theory. Within this approach we solve numerically the Poisson-Boltzmann equation for the mean electrostatic potential and minimize the Poisson-Boltzmann-Flory free energy with respect to the size of the molecules. Such a scheme enables us to inspect the conformational and electrostatic properties of the dendrimers in equilibrium based on their response to varying the dendrimer generation. The calculations indicate that the G3-G6 dendrimers exist in the polyelectrolyte regime where absorption of counterions into the volume of the molecules is minor. Trapping of ions in the interior region becomes significant for the G7-G9 dendrimers and signals the emergence of the osmotic regime. We find that the behavior of the dendritic polyelectrolytes corresponds with the degree of ion trapping. In particular, in both regimes the polyelectrolytes are swollen as compared to their neutral counterparts and the expansion factor is maximal at the crossover generation G7.

Fine-structure transitions of interstellar atomic sulfur and silicon induced by collisions with helium.

Atomic sulfur and silicon are important constituents of the interstellar matter and are both used as tracers of the physical conditions in interstellar shocks and outflows. We present an investigation of the spin-orbit (de-)excitation of S(3P) and Si(3P) atoms induced by collisions with helium with the aim to improve the determination of atomic sulfur and silicon abundances in the interstellar medium from S and Si emission spectra. Quantum-mechanical calculations have been performed in order to determine rate coefficients for the fine-structure transitions in the 5-1000 K temperature range. The scattering calculations are based on new highly correlated ab initio potentials. The theoretical results show that the (de-)excitation of Si is much faster than that of S. The rate coefficients deduced from this study are in good agreement with previous experimental and theoretical findings despite some deviations at low temperatures. From the computation of critical densities defined as the ratios between Einstein coefficients and the sum of the relevant collisional de-excitation rate coefficients, we show that local thermodynamic equilibrium conditions are not fulfilled for analyzing S and Si emission spectra observed in the interstellar medium. Hence, the present rate coefficients will be extremely useful for the accurate determination of interstellar atomic sulfur and silicon abundances.

A new ab initio potential energy surface for the NH-He complex.

We present a new three-dimensional potential energy surface (PES) for the NH(X3Σ-)-He van der Waals system, which explicitly takes into account the NH vibrational motion. The NH-He PES was obtained using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations. The augmented correlation-consistent aug-cc-pVXZ (X = Q, 5, 6) basis sets were employed, and the energies obtained were then extrapolated to the complete basis set limit. Using this new PES, we have studied the spectroscopy of the NH-He complex and we have determined a new rotational constant that agrees well with the available experimental data. Collisional excitation of NH(X3Σ-) by He was also studied at the close-coupling level. Calculations of the collisional excitation cross sections of the fine-structure levels of NH by He were performed for energies up to 3500 cm-1, which yield, after thermal average, rate coefficients up to 350 K. The calculated rate coefficients are compared with available experimental measurements at room temperature, and a reasonably good agreement is found between experimental and theoretical data.

Experimental and theoretical studies of the Xe-OH(A/X) quenching system.

New multi-reference, global ab initio potential energy surfaces (PESs) are reported for the interaction of Xe atoms with OH radicals in their ground X2Π and excited A2Σ+ states, together with the non-adiabatic couplings between them. The 2A' excited potential features a very deep well at the collinear Xe-OH configuration whose minimum corresponds to the avoided crossing with the 1A' PES. It is therefore expected that, as with collisions of Kr + OH(A), electronic quenching will play a major role in the dynamics, competing favorably with rotational energy transfer within the 2A' state. The surfaces and couplings are used in full three-state surface-hopping trajectory calculations, including roto-electronic couplings, to calculate integral cross sections for electronic quenching and collisional removal. Experimental cross sections, measured using Zeeman quantum beat spectroscopy, are also presented here for comparison with these calculations. Unlike similar previous work on the collisions of OH(A) with Kr, the surface-hopping calculations are only able to account qualitatively for the experimentally observed electronic quenching cross sections, with those calculated being around a factor of two smaller than the experimental ones. However, the predicted total depopulation of the initial rovibrational state of OH(A) (quenching plus rotational energy transfer) agrees well with the experimental results. Possible reasons for the discrepancies are discussed in detail.

Effects of chair vibration on indoor annoyance ratings of sonic booms.

The effects of perceptible whole-body vibrations on annoyance ratings of sonic booms and other impulsive environmental sounds experienced indoors were studied. Fifteen pairs of test subjects made annoyance ratings while seated in a living room environment. There were two chairs, one isolated from floor vibrations and the other not isolated, and every test subject rated all signals in both chairs. Halfway through each test session, subjects changed seats. Subjects who sat in the isolated chair first gave lower mean annoyance ratings in both halves of the test than subjects who sat in the non-isolated chair first. Annoyance predictions from models using both sound and vibration measures were closer to average annoyance ratings than predictions from a model using sound measures alone. Reformulation of the annoyance model revealed that the presence of perceptible vibration is equivalent to increasing acoustic metric Perceived Level by 4.8 dB when calculated on exterior signals and by 5.6 dB when calculated on interior signals.

Dendrimer solutions: a Monte Carlo study.

We study the conformational properties of dendrimers with flexible spacers in solutions over a wide range of concentrations from dilute solutions to melts. By combining large scale computer simulations using the bond fluctuation model with scaling arguments we identify the semi-dilute regime of dendrimers which is controlled by the concentration behavior of the linear spacers. Associated with this observation we find that the decrease in the size of flexible dendrimers is accompanied by increasing interpenetration between the molecules with increasing concentration of the solution. In the melt state we show that the size of individual dendrimers follows the scaling prediction for isolated dendrimers at the θ-point rather than that of collapsed dendrimers. The pair correlation functions between the centers of dendrimers indicate that for short spacers dendrimer solutions retain the morphological characteristics of simple liquids. For long spacers the functions reveal high penetration of neighboring dendrimers in the melt state. Our studies show that flexible dendrimers in solution can be understood with arguments similar to those of linear polymers. The role of generation is to influence the particular form of the crossover-function.

The near-IR spectrum of NO(X̃(2)Π)-Ne detected through excitation into the Ã-state continuum: A joint experimental and theoretical study.

We present new measurements of the near IR spectrum of NO-Ne in the region of the first NO overtone transition. The IR absorption is detected by exciting the vibrationally excited complex to the Ã-state dissociation continuum. The resulting NO(A) fragment is subsequently ionized in the same laser pulse. Spectra of the two lowest bands, A and B, are recorded. The spectra are compared with calculated spectra based on bound states derived from a new set of high level ab initio potential energy surfaces (PESs). For the calculation, the PESs are used with either fixed NO intermolecular distance or averaged for the vibrational states of NO (X̃, v = 0 or 2). Spectra based on the new PESs reproduce the experimental spectra better than theoretical spectra based on the older PESs of M. H. Alexander et al. [J. Chem. Phys. 114, 5588 (2001)]. Especially, spectra based on the two different vibrationally averaged PESs show a marked improvement in comparison to the one based on the fixed internuclear NO-distance. A fitted set of spectroscopic constants allows to reproduce most of the finer details of the measured spectra. Monitoring simultaneously the NO fragment ion and the parent ion channels while scanning the UV wavelength through the NO A-X hot-band region enabled us to confirm the NO-Ne Ã-state dissociation limit of 44233 ± 5 cm(-1). These measurements also confirm the absence of a structured NO-Ne spectrum involving the Ã-state.

The near-IR spectrum of NO(X̃2Π)-He detected through excitation into the Ã-state continuum: A joint experimental and theoretical study.

We present the first measurement of a bound-state spectrum of the NO-He complex. The recorded spectrum is associated with the first overtone transition of the NO moiety. The IR absorption is detected by exciting the vibrationally excited complex to the Ã-state dissociation continuum. The resulting NO(A) fragment is subsequently ionized in the same laser pulse. We recorded two bands centered around the NO monomer rotational lines, Q11(0.5) and R11(0.5), consistent with an almost free rotation of the NO fragment within the complex. The origin of the spectrum is found at 3724.06 cm-1 blue shifted by 0.21 cm-1 from the corresponding NO monomer origin. The rotational structures of the spectrum are found to be in very good agreement with calculated spectra based on bound states derived from a set of high level ab initio potential energy surfaces [Klos et al. J. Chem. Phys. 112, 2195 (2000)].

Reduced Number of CD8+ Cells in Tonsillar Germinal Centres in Children with the Periodic Fever, Aphthous Stomatitis, Pharyngitis and Cervical Adenitis Syndrome.

The syndrome of periodic fever, aphthous stomatitis, pharyngitis and cervical adenitis (PFAPA) is an autoinflammatory disorder of unknown aetiology. Tonsillectomy may cause a prompt resolution of the syndrome. The aim was to study the histologic and immunological aspects of the palatine tonsils in PFAPA, to help understand the pathophysiology of the syndrome. Tonsils from children with PFAPA (n = 11) and children with tonsillar hypertrophy (n = 16) were evaluated histologically after haematoxylin and eosin staining. The number of different cell types was identified immunohistochemically by cluster of differentiation (CD) markers: CD3 (T cells), CD4 (T helper cells), CD8 (cytotoxic T cells), CD15 (neutrophils), CD20 (B cells), CD45 (all leucocytes), CD57 (NK cells) and CD163 (monocytes and macrophages). Tonsils from children with PFAPA showed reactive lymphoid hyperplasia dominated by well-developed germinal centres with many tingible body macrophages. The histologic findings were unspecific, and a similar morphologic appearance was also found in the tonsils from controls. The number of CD8+ cells in germinal centres differed between children with PFAPA [median 9 cells (quartiles: 5, 15)] and controls [18 cells (12, 33) (P = 0.001)] and between children with PFAPA with (median 14 cells; 9, 16) and without (4 cells; 3, 8) aphthous stomatitis (P = 0.015). For the other cell types, no differences in germinal centres were found between children with PFAPA and controls. In conclusion, a lower number of CD8+ cells were found in germinal centres of tonsils in children with PFAPA compared to controls, which may be a feature linked to the aetiology of the syndrome.

Accurate Time-Dependent Wave Packet Calculations for the O(+) + H2 → OH(+) + H Ion-Molecule Reaction.

Accurate quantum reactive scattering time-dependent wave packet close-coupling calculations have been carried out to determine total reaction probabilities and integral cross sections for the O(+) + H2 → OH(+) + H reaction in a range of collision energies from 10(-3) eV up to 1.0 eV for the H2 rovibrational states (v = 0; j = 0, 1, 2) and (v = 1; j = 0) using the potential energy surface (PES) by Martínez et al. As expected for a barrierless reaction, the reaction cross section decays rapidly with collision energy, Ec, following a behavior that nearly corresponds to that predicted by the Langevin model. Rotational excitation of H2 into j = 1, 2 has a very moderate effect on reactivity, similarly to what happens with vibrational excitation below Ec ≈ 0.3 eV. However, at higher collision energies the cross section increases notably when H2 is promoted to v = 1. This effect is explained by resorting to the effective potentials in the entrance channel. The integral cross sections have been used to calculate rate constants in the temperature range 200-1000 K. A good overall agreement has been found with the available experimental data on integral cross sections and rate constants. In addition, time-independent quantum mechanical and quasi-classical trajectory (QCT) calculations have been performed on the same PES aimed to compare the various methodologies and to discern the detailed mechanism of the title reaction. In particular, the analysis of individual trajectories has made it possible to explain, in terms of the coupling between reagent relative velocity and the topography of the PES, the presence of a series of alternating maxima and minima in the collision energy dependence of the QCT reaction probabilities for the reactions with H2(v=0,1,j=0), which are absent in the quantum mechanical calculations.

Surface-hopping trajectories for OH(A(2)Σ(+)) + Kr: extension to the 1A″ state.

We present a new trajectory surface hopping study of the rotational energy transfer and collisional quenching of electronically excited OH(A) radicals by Kr. The trajectory surface hopping calculations include both electronic coupling between the excited 2(2)A' and ground 1(2)A' electronic states, as well as Renner-Teller and Coriolis roto-electronic couplings between the 1(2)A' and 1(2)A″, and the 2(2)A' and 1(2)A″ electronic states, respectively. The new calculations are shown to lead to a noticeable improvement in the agreement between theory and experiment in this system, particularly with respect to the OH(X) rotational and Λ-doublet quantum state populations, compared with a simpler two-state treatment, which only included the electronic coupling between the 2(2)A' and 1(2)A' states. Discrepancies between the predictions of theory and experiment do however remain, and could arise either due to errors in the potential energy surfaces and couplings employed, or due to the limitations in the classical treatment of non-adiabatic effects.

Fully quantum state-resolved inelastic scattering of NO(X) + Kr: differential cross sections and product rotational alignment.

Fully quantum state selected and resolved inelastic scattering of NO(X) by krypton has been investigated. Initial Λ-doublet state selection is achieved using an inhomogeneous hexapole electric field. Differential cross sections and even-moment polarization dependent differential cross sections have been obtained at a collision energy of 514 cm(-1) for both spin-orbit and parity conserving and changing collisions. Experimental results are compared with those obtained from quantum scattering calculations and are shown to be in very good agreement. Hard shell quantum scattering calculations are also performed to determine the effects of the different parts of the potential on the scattering dynamics. Comparisons are also made with the NO(X) + Ar system.

The collisional depolarization of OH(A (2)Σ(+)) and NO(A (2)Σ(+)) with Kr.

Quantum beat spectroscopy has been used to measure rate coefficients at 300 K for collisional depolarization for NO(A (2)Σ(+)) and OH(A (2)Σ(+)) with krypton. Elastic depolarization rate coefficients have also been determined for OH(A) + Kr, and shown to make a much more significant contribution to the total depolarization rate than for NO(A) + Kr. While the experimental data for NO(A) + Kr are in excellent agreement with single surface quasiclassical trajectory (QCT) calculations carried out on the upper 2A(') potential energy surface, the equivalent QCT and quantum mechanical calculations cannot account for the experimental results for OH(A) + Kr collisions, particularly at low N. This disagreement is due to the presence of competing electronic quenching at low N, which requires a multi-surface, non-adiabatic treatment. Somewhat improved agreement with experiment is obtained by means of trajectory surface hopping calculations that include non-adiabatic coupling between the ground 1A(') and excited 2A(') states of OH(X/A) + Kr, although the theoretical depolarization cross sections still significantly overestimate those obtained experimentally.

Near-IR spectrum of NO(X2Π)-Xe: a joint experimental-theoretical investigation.

Employing the method of constant photon energy sum (CONPHOENERS) scans, we measure the near-IR spectrum of NO-Xe in the region of the first vibrational overtone of the NO monomer. Three bands are detected, which are assigned as the origin band located at 3722.60 cm(-1) and as bands with excitation of one quantum of z-axis rotation (3726.07 cm(-1)) and one quantum of bending vibration (3739.02 cm(-1)), respectively. The partially resolved rotational and electronic fine structures of the bands are analyzed with the help of a full quantum mechanical bound-state calculation using the ab initio potential energy surfaces of Klos et al. (J. Chem. Phys. 2012, 137, 014312/1-014312/14). We perform a linear least-squares fit to the calculated energy levels to determine a set of spectroscopic constants that describe not only the overall rotation of the complex but also the electrostatic splitting due to the sum potential and the P-type doubling due to the difference potential. Using these results as guidance, we are able to simulate the experimental spectra. The comparison with the results from the theoretical treatment confirms the high quality of the ab initio treatment. The position of the excited bands is predicted with sub-wavenumber accuracy. Also, the rotational constants for all bands are found within less than 5%. Some differences are found for the amount of P-type doubling, which is overestimated by the theoretical treatment. Constants for the electrostatic splitting are in reasonable agreement for the origin band. Larger deviations are found for the vibrationally excited band, which points toward some inaccuracies in the potential energy surfaces.

Adsorption of branched and dendritic polymers onto flat surfaces: a Monte Carlo study.

Using Monte Carlo simulations based on the bond fluctuation model we study the adsorption of starburst dendrimers with flexible spacers onto a flat surface. The calculations are performed for various generation number G and spacer length S in a wide range of the reduced temperature τ as the measure of the interaction strength between the monomers and the surface. Our simulations indicate a two-step adsorption scenario. Below the critical point of adsorption, τc, a weakly adsorbed state of the dendrimer is found. Here, the dendrimer retains its shape but sticks to the surface by adsorbed spacers. By lowering the temperature below a spacer-length dependent value, τ*(S) < τc, a step-like transition into a strongly adsorbed state takes place. In the flatly adsorbed state the shape of the dendrimer is well described by a mean field model of a dendrimer in two dimensions. We also performed simulations of star-polymers which display a simple crossover-behavior in full analogy to linear chains. By analyzing the order parameter of the adsorption transition, we determine the critical point of adsorption of the dendrimers which is located close to the critical point of adsorption for star-polymers. While the order parameter for the adsorbed spacers displays a critical crossover scaling, the overall order parameter, which combines both critical and discontinuous transition effects, does not display simple scaling. The step-like transition from the weak into the strong adsorbed regime is confirmed by analyzing the shape-anisotropy of the dendrimers. We present a mean-field model based on the concept of spacer adsorption which predicts a discontinuous transition of dendrimers due to an excluded volume barrier. The latter results from an increased density of the dendrimer in the flatly adsorbed state which has to be overcome before this state is thermodynamically stable.

Forbidden band gaps in the spin-wave spectrum of a two-dimensional bicomponent magnonic crystal.

The spin-wave band structure of a two-dimensional bicomponent magnonic crystal, consisting of Co nanodisks partially embedded in a Permalloy thin film, is experimentally investigated along a high-symmetry direction by Brillouin light scattering. The eigenfrequencies and scattering cross sections are interpreted using plane wave method calculations and micromagnetic simulations. At the boundary of both the first and the second Brillouin zones, we measure a forbidden frequency gap whose width depends on the magnetic contrast between the constituent materials. The modes above and below the gap exhibit resonant spin-precession amplitudes in the complementary regions of periodically varying magnetic parameters. Our findings are key to advance both the physics and the technology of band gap engineering in magnonics.

The Faraday effect of natural and artificial ferritins.

Measurements of the Faraday rotation at room temperature over the light wavelength range of 300-680 nm for horse spleen ferritin (HSF), magnetoferritin with different loading factors (LFs) and nanoscale magnetite and Fe(2)O(3) suspensions are reported. The Faraday rotation and the magnetization of the materials studied present similar magnetic field dependences and are characteristic of a superparamagnetic system. The dependence of the Faraday rotation on the magnetic field is described, excluding HSF and Fe(2)O(3), by a Langevin function with a log-normal distribution of the particle size allowing the core diameters of the substances studied to be calculated. It was found that the specific Verdet constant depends linearly on the LF. Differences in the Faraday rotation spectra and their magnetic field dependences allow discrimination between magnetoferritin with maghemite and magnetite cores which can be very useful in biomedicine.

The effect of parity conservation on the spin-orbit conserving and spin-orbit changing differential cross sections for the inelastic scattering of NO(X) by Ar.

The fully Λ-doublet resolved state-to-state differential cross sections (DCSs) for the collisions of NO(X, (2)Π, v = 0, j = 0.5) with Ar have been shown to depend sensitively on the conservation of the total parity of the NO molecular wavefunction. Parity changing collisions exhibit a single maximum only in the DCS, while parity conserving transitions exhibit multiple rainbow peaks. This behaviour is shown to arise directly from the constructive or destructive interference of collisions impacting on the two pointed ends and on the flatter middle of the NO molecule. A simple hard shell, four path model has been employed to determine the relative phase shifts of the paths contributing to the scattering amplitude. The model calculations using the V(sum) potential, together with the results of a quasi-quantum treatment, provide good qualitative agreement with the experimental spin-orbit conserving (ΔΩ = 0) DCSs, suggesting that the dynamics for all but the lowest Δj transitions are determined largely by the repulsive part of the potential. The collisions leading to spin-orbit changing transitions (ΔΩ = 1) have been also found to be dominated by repulsive forces, even for the lowest Δj values. However, they are less well reproduced by hard shell calculations, because of the crucial participation of the V(diff) potential in determining the outcome of these collisions.

Fully Λ-doublet resolved state-to-state differential cross-sections for the inelastic scattering of NO(X) with Ar.

Fully Λ-doublet resolved state-to-state differential cross-sections (DCSs) for the collisions of the open-shell NO(X, (2)Π(1/2), ν = 0, j = 0.5) molecule with Ar at a collision energy of 530 cm(-1) are presented. Initial state selection of NO(X, (2)Π(1/2), j = 0.5, f) was performed using a hexapole so that the (low field seeking) parity of ε = -1, corresponding to the f component of the Λ-doublet, could be selected uniquely. Although the Λ-doublet levels lie very close in energy to one another and differ only in their relative parities, they exhibit strikingly different DCSs. Both spin-orbit conserving and spin-orbit changing collisions have been studied, and the previously unobserved structures in the fully quantum state-to-state resolved DCSs are shown to depend sensitively on the change in parity of the wavefunction of the NO molecule on collision. In all cases, the experimental data are shown to be in excellent agreement with rigorous quantum mechanical scattering calculations.