Systematic Control of Size and Morphology in the Synthesis of Gold Nanoparticles

The synthesis of gold nanoparticles (Au NPs) capped by poly(1‐vinylpyrrolidin‐2‐one (PVP, average  = 10 000 kDa) yields moderately dispersed (6–8.5 nm) product with limited morphological control while larger NPs (15–20 nm) are reliably prepared using trisodium citrate (Na₃Cit) as a reductant/capping agent. Excellent size control in the intermediate 10 nm regime is achieved by hybridizing these methodologies, with highly monodisperse, polycrystalline Au NPs forming. For a Na₃Cit:PVP:Au ratio of 3.5:3.5:1, anisotropic NPs with an aspect ratio of 1.8:1 suggest the systematic agglomeration of NP pairs. Enhanced control of NP morphology is allowed by the 1,2‐tetradecanediol reduction of Au^III in the presence of straight chain, molecular anti‐agglomerants. Last, ligand substitution is used to controllably grow preformed Au seeds. In spite of the extended growth phase used, the replacement of phosphine by 1‐pentadecylamine affords highly monodisperse, cuboidal NPs containing a single clearly visible twinning plane. The allowance of particle growth parallel to this close‐packed plane explains the remarkable particle morphology.     

Identifying Particle Correlations in Quantum Hall Regime

We introduce a method that allows the disclosure of correlations between particle positions in an arbitrary many‐body system. The method is based on a well‐known simulated annealing algorithm and the proposed artificial distribution technique. Additionally, we investigate correlations in quantum Hall liquids (we consider many‐body wave functions that have been recently determined via the cyclotron subgroup model) and present three‐dimensional plots of configuration probability distributions that have been established from numerical simulations. We demonstrate that the preferred simultaneous positions of particles (configurations of positions, which correspond to large values of a system's probability distribution, ) tend to form complicated geometric structures, which are equivalent to classical Wigner crystals only for Laughlin states. Furthermore, we claim that quantum Hall liquids attributed to non‐Laughlin fillings are correlated on subdomains rather than on a whole particle domain (due to a quantizing magnetic field, which modifies the topology of a system's dynamics). Finally, we characterize Hall‐like internal orders in terms of statistical correlations (one‐dimensional unitary representations of cyclotron subgroups). Our conclusions concerning the stability of many‐body states agree with transport measurements and various numerical studies.     

Multidimensional Particle Size Distributions and Their Application to Nonspherical Particle Systems in Two Dimensions

Particle science and technology evolve toward ever increasing complexity with respect to the multidimensional particle properties of size, shape, surface, internal structure, and composition. In this study, the theoretical background is elaborated for multidimensional particle size distributions (PSDs) by transferring the concepts known from 1D size distributions to anisotropic particles comprising at least two different length dimensions, e.g., nanorods and platelets. After introducing 2D PSDs, the calculation of differently weighted probability density functions including their interconversion is presented. This is necessary in order to compare data resulting from different measurement techniques which probe different physical properties and thus provide differently weighted PSDs. In addition, it is shown how 1D distributions with reduced content of information can be deduced from 2D PSDs. As a proof‐of‐concept and for illustration purposes, this approach is applied to a 2D Gaussian size distribution. Furthermore, a generalized scheme is suggested which outlines the conversion of number, surface, and volume weighted densities within the 2D space. The application of these methods to the more general n‐dimensional case is straightforward.     

Theory of the Robin quantum wall in a linear potential. II. Thermodynamic properties

A theoretical analysis of the thermodynamic properties of the Robin wall characterized by the extrapolation length Λ in the electric field that pushes the particle to the surface is presented both in the canonical and two grand canonical representations and in the whole range of the Robin distance with the emphasis on its negative values which for the voltage‐free configuration support negative‐energy bound state. For the canonical ensemble, the heat capacity at exhibits a nonmonotonic behavior as a function of the temperature T with its pronounced maximum unrestrictedly increasing for the decreasing fields as and its location being proportional to . For the Fermi‐Dirac distribution, the specific heat per particle is a nonmonotonic function of the temperature too with the conspicuous extremum being preceded on the T axis by the plateau whose magnitude at the vanishing is defined as , with N being a number of the particles. The maximum of is the largest for and, similar to the canonical ensemble, grows to infinity as the field goes to zero. For the Bose‐Einstein ensemble, a formation of the sharp asymmetric feature on the ‐T dependence with the increase of N is shown to be more prominent at the lower voltages. This cusp‐like dependence of the heat capacity on the temperature, which for the infinite number of bosons transforms into the discontinuity of , is an indication of the phase transition to the condensate state. Some other physical characteristics such as the critical temperature and ground‐level population of the Bose‐Einstein condensate are calculated and analyzed as a function of the field and extrapolation length. Qualitative and quantitative explanation of these physical phenomena is based on the variation of the energy spectrum by the electric field.     

Pseudogap in the Eliashberg approach based on electron‐phonon and electron‐electron‐phonon interaction

The properties of the superconducting and the anomalous normal state were described by using the Eliashberg method. The pairing mechanism was reproduced with the help of the Hamiltonian, which models the electron‐phonon and the electron‐electron‐phonon interaction (EEPh). The set of the Eliashberg equations, which determines the order parameter function (φ), the wave function renormalization factor (Z), and the energy shift function (χ), was derived. It was proven that for the sufficiently large values of the EEPh potential, the doping dependence of the order parameter () has the analogous course to that observed experimentally in cuprates. The energy gap in the electron density of states is induced by Z and χ ‐ the contribution from φ is negligible. The electron density of states possesses the characteristic asymmetric form and the pseudogap is observed above the critical temperature.

     

Quantum Kinetic Theory of a Massless Scalar Model in the Presence of a Schwarzschild Black Hole

We employ quantum kinetic theory to investigate local quantum physics in the background of spherically symmetric and neutral black holes formed through the gravitational collapse. For this purpose in mind, we derive and study the covariant Wigner distribution function near to and far away from the black‐hole horizon. We find that the local density of the particle number is negative in the near‐horizon region, while the entropy density is imaginary. These pose a question whether kinetic theory is applicable in the near‐horizon region. We elaborate on that and propose a possible interpretation of how this result might nevertheless be self‐consistently understood.     

Constraints via the Event Horizon Telescope for Black Hole Solutions with Dark Matter under the Generalized Uncertainty Principle Minimal Length Scale Effect

Four spherically symmetric but non-asymptotically flat black hole solutions surrounded with spherical dark matter distribution perceived under the minimal length scale effect is derived via the generalized uncertainty principle. Here, the effect of this quantum correction, described by the parameter $\gamma$, is considered on a toy model galaxy with dark matter and the three well-known dark matter distributions: the cold dark matter, scalar field dark matter, and the universal rotation curve. The aim is to find constraints to $\gamma$ by applying these solutions to the known supermassive black holes: Sagittarius A (Sgr. A*) and Messier 87* (M87*), in conjunction with the available Event Horizon telescope. The effect of $\gamma$ is then examined on the event horizon, photonsphere, and shadow radii, where unique deviations from the Schwarzschild case are observed. As for the shadow radii, bounds are obtained for the values of $\gamma$ on each black hole solution at $3\sigma$ confidence level. The results revealed that under minimal length scale effect, black holes can give positive (larger shadow) and negative values (smaller shadow) of $\gamma$, which are supported indirectly by laboratory experiments and astrophysical or cosmological observations, respectively.     

Multi‐Party Semi‐Quantum Key Distribution Protocol With Four‐Particle Cluster States

The application of semi‐quantum conception can provide unconditional secure communication for communicators without quantum capabilities. A semi‐quantum key distribution (SQKD) protocol based on four‐particle cluster states is put forward, which can achieve key distribution among one quantum party and two classical parties simultaneously. Furthermore, this protocol can be expanded to the χ‐party ( $\chi >3$) communication scheme. Compared with the existing multi‐party SQKD protocol, the proposed protocol and the extended one own more excellent time efficiency and qubit efficiency. The security of the proposed SQKD protocol under ideal circumstances is validated while the key rate under non‐ideal conditions is calculated.     

Theoretical kinetic study on the decomposition of 1,5‐diaminotetrazole

1,5‐Daminotetrazole (DAT) is of much interest because of the practical significance and the diversity of characteristics. The study on the decomposition pathway and the kinetics of DAT has been performed based on the quantum chemistry theory. The minimum energy path (MEP) calculation has shown that NH₂N₃ and NH₂CN are the initially detected products of DAT. And the structures of reactant, products and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods. The calculation results indicated that the energy barrier of decomposition reaction is 47.98 kcal mol^?1 and the variational effect is small. In addition, the rate constants and the Arrhenius experience formula of DAT decomposition have been obtained between 200 and 2500 K temperature regions. The fitted three‐parameter expressions calculated using the TST and CVT methods are (TST) and (CVT). This work may provide the theoretical support for further experimental synthesis and testing. Copyright © 2015 John Wiley & Sons, Ltd.     

Nonlinear absorption and refraction in crystalline silicon in the mid‐infrared

The wavelength dependence of the nonlinear absorption and the third order nonlinear refraction of crystalline silicon between m and m as well as at m have been measured. It was found that at all wavelengths multi‐photon and free carrier absorption can be significant. In particular nonlinear absorption can affect silicon devices designed for the mid‐infrared that require strong nonlinear response, such as for the generation of a supercontinuum.     

Dust in Plasma I. Particle Size and Ion‐Neutral Collision Effects

A fully kinetic self‐consistent model of an absorbing particle immersed in stationary isotropic weakly collisional plasma has been developed. The combined effects of particle size and ion‐neutral charge exchange collisions have been investigated for intermediate regimes, where no analytic theories are available. It is shown that collisional effects related to the ion orbital destruction (presence of extrema in ion flux collected on the particle surface and in particle potential and charge) are important for small particles, while they are totally absent for large particles. The potential distribution around the particle is quite well represented by a Yukawa form, but with an effective screening length that shows different dependences from the gas pressure for small and large particle size. Analytical fitting formulas of particle charge and potential and screening length depending on the particle radius parameter and on the Knudsen number have been obtained (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gas‐phase acidity of bis[(perfluoroalkyl)sulfonyl]imides. Effects of the perfluoroalkyl group on the acidity

The gas‐phase acidity (GA) values were determined for a number of perfluoroalkyl‐substituted sulfonylimides by measuring proton‐transfer equilibria using a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer. The GA scale below 286.5 kcal mol^?1 for (CF₃SO₂)₂NH was extended and partially revised. The GA value of (C₄F₉SO₂)₂NH which is currently the strongest acid was revised from 284.1 to 278.6 kcal mol^?1. The effect of fluorine atoms on the acidity of perfluoroalkyl‐substituted sulfonylimides was described with the following model where N_(α), N_(β), N_(γ), and N_(δ) are the numbers of fluorine atoms at α, β, γ, and δ position in R_fSO₂ (R_f = perfluoroalkyl group), respectively. This correlation indicates that the electron‐withdrawing ability of the R_fSO₂ group can be described in terms of the number of fluorine atoms in the perfluoroalkyl group corrected by taking into account their positions. Copyright © 2014 John Wiley & Sons, Ltd.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Towards a world‐sheet description of doubled geometry in string theory

Starting from a sigma‐model for a doubled target‐space geometry, we show that the number of target‐space dimensions can be reduced by half through a gauging procedure. We apply this formalism to a class of backgrounds relevant for double field theory, and illustrate how choosing different gaugings leads to string‐theory configurations T‐dual to each other. We furthermore discuss that given a conformal doubled theory, the reduced theories are conformal as well. As an example we consider the three‐dimensional WZW model and show that the only possible reduced backgrounds are the cigar and trumpet CFTs in two dimensions, which are indeed T‐dual to each other.     

Investigation of the vibrational modes of ZnO grown by MOCVD on different orientation planes

Wurtzite ZnO thin films were prepared on sapphire substrate by metal organic chemical vapor deposition (MOCVD). Raman scattering studies on different crystallographic textures were performed in the backscattering geometry, and polarization effect is investigated in different configurations and . ZnO Raman modes are investigated in each texture. In the case of ZnO thin film deposed on r‐() sapphire plane and using backscattering geometry, new Raman line was observed at 390 cm⁻¹ because this mode has not been noticed in this geometry. It is shown that the frequencies of the quasi‐phonon modes of the examined thin film are in good agreement with the theoretical values calculated within the framework of Loudon model. Copyright © 2014 John Wiley & Sons, Ltd.     

Determining the excited‐state substituent constants of furyl and thienyl groups

Six series of styrene derivatives XCH═CHArY (total of 65) containing the styrene parent molecular skeleton were synthesized (here, Y is OMe, Me, H, F, Cl, CF₃, CN, and NO₂, and X is 2‐furyl, 3‐furyl, 2′‐methyl‐2‐furyl, 2‐thienyl, 3‐thienyl, and 2′‐methyl‐2‐theniyl). Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelength of absorption maximum λ_max was recorded. For the wavenumber ν_max (cm^?1, ν_max = 1/λ_max) of the obtained λ_max, a quantitative correlation analysis was performed, and 6 excited‐state substituent constants of groups X were obtained by means of curve‐fitting method. Taking the ν_max values of total 90 compounds of styrene derivatives as a data set (including 25 compounds from reference and 65 compounds of this work), a quantitative correlation analysis was performed, and the reliability of the obtained was verified. In addition, 12 samples of disubstituted Schiff bases (XCH═NArY) involving the above groups X were synthesized, and their ν_max values were recorded. Using these 12 ν_max together with the 14 ν_max values of Schiff bases taken from reference (total of 26 compounds), it was further verified that the values are reliable by means of quantitative correlation method.