Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T < 10 K. For this complex, the structure is identified and the distance between the copper ions is determined. It is shown that the nitrate counterion plays the role of a bridge between the hexaaqua copper(II) complex and the dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO₄) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B ₀ = 8000 G). The degree of orientation of these complexes is rather high (S _z = 0.76) and close to that of systems with a complete ordering (S _z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH₄, N₂H₄ · H₂O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.     

Spectral characteristics of a barrier discharge in cadmium dihalide vapor-inert gas mixtures

Spectral characteristics of a barrier-discharge plasma produced in atmospheric-pressure mixtures of cadmium diiodide and cadmium dibromide vapors with neon, krypton, and xenon at a repetition rate of sine voltage pulses up to 130 kHz are studied. The emission from the discharge is studied within the spectral range 200–900 nm with a resolution of 0.05 nm. Emission of exciplex molecules CdI(B → X) and CdBr(C, B → X), and cadmium and inert gas atoms is revealed, as well as emission of exciplex molecules XeI(B → X, A) and XeBr(B → X, A) in xenon-containing mixtures. The emission of xenon halides prevails in the spectra at a mixture temperature up to 200°C. With a further temperature increase, the emission of cadmium halides becomes dominating. It is ascertained that the most intense emissions of CdI(B → X) and CdI₂/CdBr₂/Xe/Kr and CdBr(B → X) molecules are observed, respectively, in CdI₂/CdBr₂/Xe/Kr and CdI₂/CdBr₂/Xe mixtures. The cadmium dihalide-inert gas mixtures are of interest for the use as a radiating gas in a multiwavelength and broadband excilamp emitting in the UV and visible spectral ranges.     

Studying reactions that proceed from highest excited states of molecules using fluorescence quenching

The steady-state monochromatic excitation of a luminophore that has fluorescing products is considered. The effect of dynamic quenching of highest excited states on the fluorescence of singlet states under its excitation via singlet S ₁ and S _n (n ≥ 2) states is discussed. It is shown that the use of the method of fluorescence dynamic quenching by foreign impurities opens new possibilities for studying photoreactions that proceed via S _n singlet states. A large number of primary photoprocesses are considered which include the electron density redistribution (the internal electron transfer) in the excited state, protolytic reactions, intramolecular proton transfer (phototautomerization), hydrogen bonding, and formation of excimers and exciplexes. It is shown that, upon dynamic quenching, the bimolecular quenching constant of an excited level depends on the amount of thermal energy released in the luminophore before the occurrence of the light emission event. Based on the experimental measurements of the fluorescence spectra at different quencher contents, the calculation of the Stern-Volmer constant for reaction products is considered in detail. It is shown that this constant can be most reliably determined from the dependence of the fluorescence intensity ratio of the initial reagents and the quencher product rather than from the dependence of the fluorescence intensity of the products on the concentration of the quencher. The relations determined are used in analysis of the experimental fluorescence spectra of solutions of 3-hydroxyflavone excited by radiation with different wavelengths lying in the range of the S ₁ and S ₂ absorption bands. The temperature behavior of the Stern-Volmer constant for different fluorescence bands of 3-hydroxyflavone is considered. It is shown that, if these constants for the normal and tautomeric forms are correctly determined, their temperature dependences are similar.     

Spherical Symmetric Perfect Fluid Collapse in <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>, <Emphasis Type="Italic">T</Emphasis>) Gravity

This paper contains the study of spherically symmetric perfect fluid collapse in the frame work of f(R, T) modified theory of gravity. We proceed our work by considering the non-static spherically symmetric background in the interior and static spherically symmetric background in the exterior regions of the star. The junction conditions between exterior and interior regions are presented by matching the exterior and interior regions. The field equations are solved by taking the assumptions that the Ricci scalar as well as the trace of energy-momentum tensor are to be constant, for a particular f(R, T) model. By inserting the solution of the field equations in junction conditions, we evaluate the gravitational mass of the collapsing system. Also, we discuss the apparent horizons and their time formation for different possible cases. It is concluded that the term f(R ₀, T ₀) behaves as a source of repulsive force and that’s why it slowdowns the collapse of the matter.     

Dark matter from the SU(4) model

The left-right symmetric Pati-Salam model of the unification of quarks and leptons is based on the SU(4) and SU(2)×SU(2) symmetry groups. These groups are naturally extended to include the classification of families of quarks and leptons. We assume that the family group (the group which unites the families) is also the SU(4) group. The properties of the fourth generation of fermions are the same as those of the ordinary-matter fermions in the first three generations except for the family charge of the SU(4)_F group: F=(1/3, 1/3, 1/3, ?1), where F=1/3 for fermions of ordinary matter and F=?1 for the fourth-generation fermions. The difference in F does not allow mixing between ordinary and fourth-generation fermions. Because of the conservation of the Fcharge, the creation of baryons and leptons in the process of electroweak baryogenesis must be accompanied by the creation of fermions of the fourth generation. As a result, the excess n _B of baryons over antibaryons leads to the excess n_4ν=N?N? of neutrinos over antineutrinos in the fourth generation with n_4ν=n _B . This massive neutrino may form nonbaryonic dark matter. In principle, the mass density of the fourth neutrino n_4νm _N in the Universe can make the main contribution to dark matter, since the lower bound on the neutrino mass m _N from the data on decay of the Z bosons is m _N <m _Z /2. The straightforward prediction of this model leads to the amount of cold dark matter relative to baryons, which is an order of magnitude higher than allowed by observations. This inconsistency may be avoided by nonconservation of the F charge.     

Doppelkonversion

An excited nuclear state can decay by three different modes of double quantum emission, namely doubleγ-emission,γ-electron emission and double conversion electron emission. The emission of twoγ-quanta has been considered in an earlier paper¹. The purpose of the present work is to treat all three processes together in a systematic manner. It is shown that the connection between the transition rates forγ-electron emissionT _γc and doubleγ-quantum emissionT _γγ is more complicated than in the case of single quantum processes. However,T _γc can still be expressed in terms of the usual conversion coefficients. This is also true for the transition rate T_cc for the emission of twoK-shell electrons, although only approximately. For the emission of electrons from different atomic shells the formulas become rather complicated, because of interference effects. The electron andγ-quantum spectra in all of the three second order processes are discussed in detail for the decay of the isomeric level in Xe¹³¹.     

Duality-mediated critical amplitude ratios for the (2 + 1)-dimensional S = 1XY model

The phase transition for the (2 + 1)-dimensional spin-S = 1XY model was investigated numerically. Because of the boson-vortex duality, the spin stiffness ρ _s in the ordered phase and the vortex-condensate stiffness ρ _v in the disordered phase should have a close relationship. We employed the exact diagonalization method, which yields the excitation gap directly. As a result, we estimate the amplitude ratios ρ _s,v /Δ (Δ: Mott insulator gap) by means of the scaling analyses for the finite-size cluster with N ≤ 22 spins. The ratio ρ _s /ρ _v admits a quantitative measure of deviation from selfduality.     

Doppler three-level (V-scheme) laser without population inversion

The theory of amplification and lasing without population inversion in a three-level medium with inhomogeneous broadening via the formation of an open V configuration is elaborated. The conditions for energy transfer from the infrared into the visible spectral range, i.e., the conditions of up-conversion n _b >n _c >n _a , and the external field required for saturation of the b?a transition are established. Two-photon resonant Raman transitions in ensemble of mobile atoms of a gas-discharge plasma are analyzed. The frequency shift of the probe field spectrum as a whole is shown to be governed by the frequency shift of the pump field multiplied by the ratio of the wave numbers of the probe amplification field and the pump field. The interaction of atoms through Ne transitions with the pump field (λ=1.15 εm, 2p ₄-2s ₂ transition) and the lasing field (λ=0.6328 εm, 3s ₂-2p ₂ transition) with an increase in the lasing frequency by a factor of 1.82 with respect to the absorbed radiation is calculated.     

Applications of a unique group embedding of internal symmetry groups andSU(2): spin-extensions for G2 and for the Sp(6)-Trion model

A recently proposed method of embeddingSU (2) and an internal symmetry groupG into a bigger groupG is applied to construct a spin extension ofG ₂ andSp (6). BecauseG ₂ andSp (6) possess a generalized quark model the embedding group can be proved to be unique and to be given bySp (14) resp.O (12) forG ₂ resp.Sp (6). For a particle classification splittings are calculated and tabulated forSp (14) ↓G ₂ xSU (2) andO (12) ↓Sp (6) xSU (2). The identification of low dimensional irreducible representations ofO (12) is quite satisfactory whereas an unreasonable number of unobserved particles are needed to fill up the supermultiplets of the spin extensionSp (14) of G₂.     

A continuous time random walk (CTRW) integro-differential equation with chemical interaction

A nonlocal-in-time integro-differential equation is introduced that accounts for close coupling between transport and chemical reaction terms. The structure of the equation contains these terms in a single convolution with a memory function M?(t), which includes the source of non-Fickian (anomalous) behavior, within the framework of a continuous time random walk (CTRW). The interaction is non-linear and second-order, relevant for a bimolecular reaction A + B → C. The interaction term ΓP _A ?(s, t)?P _B ?(s, t) is symmetric in the concentrations of A and B (i.e. P _A and P _B ); thus the source terms in the equations for A, B and C are similar, but with a change in sign for that of C. Here, the chemical rate coefficient, Γ, is constant. The fully coupled equations are solved numerically using a finite element method (FEM) with a judicious representation of M?(t) that eschews the need for the entire time history, instead using only values at the former time step. To begin to validate the equations, the FEM solution is compared, in lieu of experimental data, to a particle tracking method (CTRW-PT); the results from the two approaches, particularly for the C profiles, are in agreement. The FEM solution, for a range of initial and boundary conditions, can provide a good model for reactive transport in disordered media.     

Formation of textured Ni(200) and Ni(111) films by magnetron sputtering

The effect of the working gas pressure (P ≈ 1.33–0.09 Pa) and the substrate temperature (T_s ≈ 77–550 K) on the texture and the microstructure of nickel films deposited by magnetron sputtering onto SiO₂/Si substrates is studied. Ni(200) films with a transition type of microstructure are shown to form at growth parameters P ≈ 0.13–0.09 Pa and T_s ≈ 300–550 K, which ensure a high migration ability of nickel adatoms on a substrate. This transition type is characterized by a change of the film structure from quasi-homogeneous to quasi-columnar when a film reaches a critical thickness. Ni(111) films with a columnar microstructure and high porosity form at a low migration ability, which takes place at P ≈ 1.33–0.3 Pa or upon cooling a substrate to T_s ≈ 77 K.     

Solvatochromic effect on photophysical properties of Quinoxalin-2(1H)-one and 3-Benzylquinoxalin-2(1H)-one

Quinoxalin-2(1H)-one and its derived 3-Benzylquinoxalin-2(1H)-one were synthesized and characterized by UV–visible spectroscopy. The changes displayed by the photophysical properties of these molecules in different solvents can be explained in terms of a sum of dielectric polarity and hydrogen bonding effects taking part in the stabilisation of the structure. 3-Benzylquinoxalin-2(1H)-one exhibits two fluorescence emission bands (F _a and F _n) in very polar solvents and one band (F _n) in low polar solvents. These bands are assigned on the basis of the absorption and emission solvent effect. The abnormal fluorescence (F _a) observed in very polar solvents is attributed to an intermolecular interaction between solute and solvent molecules in the excited state (exciplex formation).     

Proton-proton interaction with high multiplicity at energy of 70 GeV (proposal)

The goal of the proposed experiment is to investigate the collective behavior of particles in the process of multiple hadron production in pp interaction pp → n _π π + 2N at the beam energy E_lab = 70 GeV. The domain of high multiplicity n _π = 30–40, or z = n/\(\bar n\) = 4–6, will be studied. Near the threshold of reaction n _π → 69, z → z_th = 8.2, all particles acquire small relative momentum Δq < 1/R, where R is the dimension of the particle production region. As a consequence of multiboson interference, a number of collective effects may show up: (a) a drastic increase in the partial cross section σ(n) of production of n identical particles is expected, compared with commonly accepted extrapolation; (b) the formation of jets consisting of identical particles may occur as a result of the multiboson Bose-Einstein correlation (BEC) effect; (c) a large fluctuation of charged n(π⁺,π^?) and neutral n(π⁰) components and onset of centauros or chiral condensate effects are anticipated; (d) an increase in the rate of direct γ as a result of the bremsstrahlung in the partonic cascade and annihilation of π⁺π^? → nγ in dense and cold pionic gas or condensate is expected. In the domain of high multiplicity z ≥ 5, a major part of the c.m. energy \(\sqrt s = 11.6\) GeV is materialized, leading to a high-density thermalized hadronic system. Under this condition, a phase transition to cold quark-gluon plasma (QGP) may occur. The search for QGP signatures like large intermittency in the phase-space particle distribution and an enhanced rate of direct photons will be performed. The experimental setup is designed for detection of rare high-multiplicity events. The experiment is to be carried out at the extracted proton beam of the IHEP U-70 accelerator. The required beam intensity is ～10⁷ s^?1. Under the assumption that the partial cross section σ(n _π = 35) = 10-1 nb, the anticipated counting rate is 10-1 events/h. The multiboson BEC enhancement may drastically increase the counting rate.     

Kinetics of pulsed cathodoluminescence

The kinetics of pulsed cathodoluminescence, which appears upon irradiation of condensed media with high-power electron beams of nanosecond duration, is analyzed. Four types of emission are considered: recombination emission, exciton emission, intracenter emission, and emission of electron and hole centers. It is found that the maximum difference in the kinetics of the intensities of emission of these types occurs in the time interval t≤t ₁≈A ^?1, and, in the far afterglow, an exponential decay occurs with the characteristic time (2A)^?1 for the first and second types of luminescence and A ^?1 for the fourth type. For the intracenter luminescence, the decay time is equal to (2A)^?1 and A _i ^?1 for short-lived and long-lived radiative levels, respectively (A and A _i are the probabilities of linear recombination of electron-hole pairs and decay of a radiative level, respectively). In the case of long-lived radiative levels, a strong peak is observed in the spectrum of intracenter luminescence in the far afterglow.     

Relations between the electromagnetic form factors of the 0−- and 1−-mesons from the collinear groupsSU(3)⊗SU(3)⊗U(1) andSU(6) W

The relations between the electromagnetic matrix elements of the 18 low lying pseudoscalar and vector mesons predicted by the collinear groupsSU(3)?SU(3)?U(1) andSU(6) _W are derived. Using the hermiticity of the electromagnetic current operator, charge conjugation invariance and invariance under the full Lorentz group andSU(3)-symmetry separately, all electromagnetic matrix elements of these mesons are described by seven independent real form factors. After combining space-time with intrinsic properties of the particles this number is reduced to four by the minimal collinear groupSU(3) ?SU(3) ?U(1) and to three bySU(6) _W which involves more speculative assumptions. In the limit of low momentum transfer the predictions of both models become identical, depending on three real quantities. No disagreement with experiment has been found, as far as a comparison is possible.     

Magnetic properties of arrays of cobalt nanoparticles on the CaF<Subscript>2</Subscript>(110)/Si(001) surface

The Co/CaF₂/Si(001) heterostructures with the corrugated (110) surface of the CaF₂ buffer layer have been grown by molecular beam epitaxy. The structures are nanoparticle arrays of single-crystal Co, mostly of the cubic fcc modification. The behavior of the magnetic hysteresis loops as a function of the density of coverage of the substrate by cobalt islands, the island size, and the temperature is studied using the magnetooptical technique. At low coverage densities, where the effective cobalt film thickness d _eff is less than the critical value d _eff ^c , the magnetic structure of the films at T = 294 K can be visualized as an ensemble of superparamagnetic, weakly interacting nanoparticles and is characterized by small values of the coercive field H _c and the remanent magnetization M _rem. A decrease in the temperature leads to a strong increase in H _c and M _rem, which is associated with the transition of the islands to the blocked state. The blocking temperature of the structures is T _b ～ 280 K. The magnetic anisotropy parameter K and the saturation magnetization M _s of the islands depend on the growth temperature of cobalt T _Co. An increase in the coverage density above the critical thickness d _iff ^c at T = 294 K brings about a strong increase in H _c and M _rem and the appearance of a hysteresis loop anisotropy originating from the corrugated structure of the CaF₂ buffer layer. The experimental results are compared with the model of an ensemble of noninteracting superparamagnetic particles.     

f(R) Black Holes as Heat Engines

With the cosmological constant considered as a thermodynamic variable in the extended phase space, it is natural to study the thermodynamic cycles of the black hole, which is conjectured to be performed using renormalization group flow. We first investigate the thermodynamic cycles of a 4-dimensional asymptotically AdS f(R) black hole. Then we study the thermodynamic cycles of higher dimensional asymptotically AdS f(R) black holes. It is found that when ΔV ? ΔP, the efficiency of isobar-isochore cycles running between high temperature T_H and low temperature T_C will increase to its maximum value, which is exactly the Carnot cycles’ efficiency both in 4-dimensional and in higher dimensional cases. We speculate that this property is universal for AdS black holes, if there is no phase transition in the thermodynamic cycle. This result may deepen our understanding of the thermodynamics of the AdS black holes.     

Atomic level energies in hafnium

The photo electron method for obtaining electron binding energies is described. The method has been applied to theL _I,L _II, andL _III levels in hafnium. The HfK α₁ and HfK α₂ x-ray emission lines have been measured with a crystal spectrometer. The electron binding energies of theK toO _III shells in hafnium are obtained from photo electron and x-ray emission data. A new type of Moseley diagram is described and is demonstrated for theK andL levels in theZ region 57 to 75. From these diagrams accurate binding energies for the element Pm (Z=61) have been obtained by interpolation.     

<Emphasis Type="Italic">M</Emphasis>α and <Emphasis Type="Italic">M</Emphasis>β X-ray emission spectra of Au atoms upon photoionization of <Emphasis Type="Italic">L</Emphasis> subshells

The structure and relative intensity of the Mα and Mβ X-ray fluorescence spectra of Au atoms are studied experimentally at the energies of absorbed photons both below and above the ionization thresholds of L subshells (Kα_{1, 2} radiation of Cr, Cu, and Mo). The M ₅ N and M ₄ N high-energy satellites are separated from the total spectral profiles and their relative intensities are determined. A model of the M emission is proposed that allows one to take into account the main channels of vacancy transfer from L to M subshells, which are responsible for the generation of double vacancy (M _{4, 5} N and M _{4, 5} O) and triple vacancy (M _{4, 5} N ², M _{4, 5} NO, and M _{4, 5} O ²) states. Comparison of the experimental relative intensities of separated M ₅ N and M ₄ N satellites excited by the Mo Kα_{1, 2} radiation with the calculated results indicates the correctness of the model used. The partial and total M emission cross sections of Au in the absorbed photon energy range of 5–30 keV are calculated. It is found that, in the photon energy region above the ionization threshold of the L ₃ subshell, our results noticeably differ from the data calculated by other authors. Possible reasons for these discrepancies are discussed.     

Study of the atom-phonon coupling model for (SC) partition function: first order phase transition for an infinite linear chain

In spin-conversion (SC) compounds containing molecules organized around an iron (II) ion the fundamental level of the ion is low spin (LS), S = 0, and its first excited one is high spin (HS), S = 2. This energy diagram is due to the ligands field interaction on 3d electrons and to the spin pairing energy. Heating the compound increases the magnetic susceptibility which corresponds to a change of populations of both levels and consequently a change of spin value of the molecules. This mechanism, called spin conversion (SC), can be accompagnied by thermal hysteresis observed by studying magnetic susceptibility or high spin fraction. In that case one considers that the (SC) takes place through a first-order phase transition due to intermolecular interactions. In the atom-phonon coupling model the molecules are considered as two-level systems, or two-level atoms, and it is assumed that the elastic force constant value of the spring which links two atoms first neighbours is depending on the electronic states of both atoms. In this study we calculate the partition function of a linear chain of N atoms (N ≤ 16) and we describe the role of phonons and that of the parameter Δ which corresponds to the distance in energy between both levels. The chain free-energy function is F _atph . We introduce for the chain a free-energy function defined by the set (F _HS , F _LS , F _barr ) and we show that F _atph tends towards the previous set when N → ∞. The previous set allows to describe a first order phase transition between a (LS) phase and a (HS) one. At the crossing point between the function F _LS and F _HS , and around this point, there is an intermediate free-energy barrier which prevents the chain to change phase which can lead to thermal hysteresis. The energy gap between the free-energy function F _atph and that defined by the set (F _HS , F _LS , F _barr ) is small. So we can expect that a nanoparticule takes for free-energy function that defined by the set and then displays a thermal hysteresis.