Do ‘Quark-Stars’ Exist?

Possible existence of quark-matter in dense neutron-stars is discussed using Quantum Chromodynamical equation of state for cold degenerate quark-matter.     

Is 4‐nitrobenzenethiol converted to p,p′‐dimercaptoazobenzene or 4‐aminothiophenol by surface photochemistry reaction?

For the first time, the experimental and theoretical evidence for the conversion of 4‐nitrobenzenethiol (4‐NBT) to p,p′‐dimercaptoazobenzene (DMAB) in Ag and Cu sols by surface photochemistry reaction is obtained with surface‐enhanced Raman scattering (SERS) spectroscopy. The SERS spectrum of 4‐NBT in Cu sol is identical to that of DMAB produced from 4‐aminothiophenol in Ag sol as reported in recent literature, thereby providing direct spectral evidence. Copyright © 2011 John Wiley & Sons, Ltd.     

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

The formation of N‐trifluoromethylsulfonyl‐2‐vinylaziridine and N‐trifluoromethylsulfonyl‐3‐pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s‐cis‐ and s‐trans‐1,3‐butadienes was studied theoretically at the B3LYP/6‐311++G(d,p) and M06‐2X/6‐311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s‐cis‐ and s‐trans‐1,3‐butadiene exothermally in one step to give the product of 1,2‐cycloaddition, N‐trifluoromethylsulfonyl‐2‐vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06‐2X level, respectively. The formed 2‐vinylaziridine can undergo rotation about the C(2)–C_sp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N‐trifluoromethylsulfonyl‐3‐pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s‐cis‐ and s‐trans‐1,3‐butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06‐2X level for the adducts to s‐cis‐ and s‐trans‐1,3‐butadiene, respectively. Recombination of the radical centers occurs selectively to give N‐trifluoromethylsulfonyl‐2‐vinylaziridine that is exothermally rearranged into N‐trifluoromethylsulfonyl‐3‐pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06‐2X level. Copyright © 2014 John Wiley & Sons, Ltd.     

Intra‐ and intermolecular N?H···O hydrogen bonds in pyrrolyl derivatives of indane‐1,3‐dione – experimental and theoretical study

2‐(Pyrrol‐2‐ylmethylene)‐1,3‐indandione ( 4 ) and 2‐(pyrrol‐2‐ylmethylene)‐3‐dicyanomethylidene‐1‐indanone ( 5 ) were synthesized. Multinuclear and 2D‐NMR, IR, UV spectroscopic investigations as well as quantum chemical calculations showed the presence of strong hydrogen bonding in these molecules. For both molecules, the presence of two conformers, with and without H‐bond, was experimentally detected in the basic solvents (DMSO, acetone, pyridine) and the solvate complexes were theoretically calculated. Specific behavior of the intramolecular H‐bonded complexes different from that of the intermolecular H‐complexes is discussed. Copyright © 2009 John Wiley & Sons, Ltd.     

Laser Diffraction – Unlimited?

Within the past 20 years, particle size analysis with laser diffraction (LD) has been subject to rapid development, extending the size range stepwise from 1–200 μm to about 0.1–3500 μm. The limits of LD are discussed in terms of light sources, the influence of the beam diameter, special Fourier optics and a new detector design. It is shown that the size range is not only restricted by the wavelength of the laser and the transmission limits of the medium. Its extension is mainly related to improvements in the measurement of the angular intensity distribution. Influences from stability and flow dominate on the coarse side of the measuring range. On the fine side, the spatial extension of aerosols and the resulting demand for extended working distances can be covered only in a parallel laser beam. Extended Fourier optics in combination with an adapatable beam expansion technique and a detector with virtual borders between semicircular elements overcome the existing limits and extend the size range to a lower limit of about 0.05 μm and an upper limit above 10 mm. The sensititivity limit of LD is approaching that of single particle counting techniques. For medical spray and inhaler applications, a 0.1% optical concentration can be converted to particle size distributions even for time-resolved analyses with sample intervals of a few milliseconds. The reproducibility of the sensor, with a standard deviation typically much less than 0.5%, is no longer the limiting factor. The reproducibility of the results is mainly dominated by the reproducibility of sampling, sample splitting, dispersion and the contamination of the optical path. The latter can be improved by the control of flow, especially for in-line and inhaler applications.     

Ψ and Υ Production in p-p Collisions at E = 5, 14 TeV; and Comparison with Experiment at E = 7 TeV

This brief report is an extension of our recent studies of Ψ and Υ production cross sections in proton-proton collisions with E \(=\sqrt {s}=13\) TeV to E = 5 and E =14 TeV, using the mixed heavy quark hybrid theory in which the Ψ(2S) and Υ(3S) are 50 % hybrid states. Also, comparison with recent experiments at E = 7 TeV are used to test the mixed heavy hybrid theory.     

Experimental study on the reaction pathway of α‐haloacetophenones with nucleophiles: direct substitution or carbonyl addition?

The reaction of PhCOCH₂Cl with OH^– gave the expected α‐substituted alcohol (PhCOCH₂OH) in addition to three dimer products. To clarify whether the substitution product is formed by direct S_N2 or via carbonyl addition, the reaction of PhCOCH₂Cl and OMe^– was examined. The reaction gave two products, PhCOCH₂OH as the major product after acid hydrolysis and PhCOCH₂OMe as the minor product. An electron‐withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was concluded that the alcohol was formed via carbonyl addition‐epoxidation route, whereas the ether was formed by the direct substitution route. Copyright © 2012 John Wiley & Sons, Ltd.     

Which Physical Quantity Deserves the Name “Quantity of Heat”?

“What is heat?” was the title of a 1954 article by Freeman J. Dyson, published in Scientific American. Apparently, it was appropriate to ask this question at that time. The answer is given in the very first sentence of the article: heat is disordered energy. We will ask the same question again, but with a different expectation for its answer. Let us imagine that all the thermodynamic knowledge is already available: both the theory of phenomenological thermodynamics and that of statistical thermodynamics, including quantum statistics, but that the term “heat” has not yet been attributed to any of the variables of the theory. With the question “What is heat?” we now mean: which of the physical quantities deserves this name? There are several candidates: the quantities Q, H, Etherm and S. We can then formulate a desideratum, or a profile: What properties should such a measure of the quantity or amount of heat ideally have? Then, we evaluate all the candidates for their suitability. It turns out that the winner is the quantity S, which we know by the name of entropy. In the second part of the paper, we examine why entropy has not succeeded in establishing itself as a measure for the amount of heat, and we show that there is a real chance today to make up for what was missed.     

Can 2‐acylpyrroles form an intramolecular hydrogen bond?

The formation of intramolecular hydrogen bonding by certain N‐substituted 2‐acylpyrroles has been demonstrated by B3LYP/aug‐cc‐pVDZ calculations, the quantum theory of atoms in molecules, and the natural bond orbital method. Total electron energy densities H_BCP at the bond critical point of the H?O bond were applied to analyze the strength of these interactions. The relations between quantum theory of atoms in molecules, carbonyl stretching vibrational modes ν_{C = O}, and natural bond orbital parameters associated with the formation of the C–H?O interaction have been established. The short contacts were found experimentally in the crystal structure of a new 2‐acylpyrrole derivative 5‐chloro‐2‐oxopentyl‐1‐(5‐chloro‐2‐oxopentyl)pyrrolo‐2‐carboxylate. The influence of 2‐ and N‐substitution of 2‐acylpyrroles on C‐H?O interaction energy is discussed. It was found that the methylene group may act as a proton donor leading to a red‐shift or blue‐shift phenomenon of the ν_C–H stretching mode. Copyright © 2015 John Wiley & Sons, Ltd.     

Ionized physical vapor deposited Al2O3 films: Does subplantation favor formation of α‐Al2O3?

The broad energy distributions of the condensing particles typically encountered in ion assisted vapor deposition techniques are often a drawback when attempting to understand the effect of the energetic bombardment on the film properties. In the current study, a monoenergetic Al⁺ beam generated by a filtered cathodic arc discharge is employed for the deposition of alumina (Al₂O₃) films at well defined Al⁺ ion energies between 4 eV and 200 eV at a substrate temperature of 720 °C. Structural analysis shows that Al⁺ energies of 40 eV or larger favor the formation of the thermodynamically stable α‐Al₂O₃ phase at the expense of other metastable Al₂O₃ polymorphs. The well defined ion energies are used as input for Monte‐Carlo based simulations of the ion–surface interactions. The results of these simulations reveal that the increase of the Al⁺ ion energy leads to an increase in the fraction of ions subplanted into the growing film. These findings underline the previously not considered role of subsurface processes on the phase formation of ionized physical vapor deposited Al₂O₃ films. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Where Is a Singer''s Voice if It Is Placed “Forward”?

Singing teachers sometimes characterize voice quality in terms of "forward" and "backward" placement. In view of our traditional knowledge about voice production it is hard to explain any possible acoustic or articulatory differences between the voices so "placed." The analysis of the teachers' expert opinions demonstrates that, in general, a voice placed "forward" indicates a desirable quality that students should attain by the end of their studies. Productions that were perceived as "forward" and "backward" were selected from the listening test. The acoustic analysis of those productions reveals that the voice quality in the case of "forward" placement correlates with higher frequencies of the second (F2) and third (F3) formants, as well as with a more salient "singer's formant" in the voice. The five basic vowels were included in the investigation.     

Momentum-dependent mean field in π<Subscript>0</Subscript> production in Nb + Nb collisions

The Boltzmann-Nordheim-Vlasov (BNV) equation has been solved by using a microscopic momentum-dependent (MD) nuclear mean field. This potential has been calculated in the framework of the self-consistent Brueckner theory up to the second order in the G-matrix. Comparison with the so-called soft and stiff Equation of State (EOS) is presented, using the Skyrme force. Calculations have been performed for the ⁹³Nb + ⁹³Nb reaction at E_lab = 100, 250, 400A MeV. Our results show that the subthreshold π₀ production cross-section is very sensitive to the momentum-dependent mean field, resulting, at the lowest energy, in a total cross-section a factor of 7 larger than that obtained with a local potential. The effect decreases as the bombarding energy increases.     

Successive structural phase transitions in Pr<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> in the range 10–1120 K

The crystal and magnetic structures of the Pr_0.5Sr_0.5CoO₃ metallic ferromagnet have been studied using neutron diffraction and synchrotron radiation. Successive structural transitions with the reduction of the crystal symmetry from cubic (space group Pm3m) to rhombohedral (\(R\bar 3c\), ～800 K), orthorhombic (Imma, ～300 K) and, then, to triclinic at ～120 K are detected during cooling from 1120 K. The transition from the orthorhombic system to a phase with a lower symmetry is characterized by a sharp change in the anisotropy of the unit cell, which indicates the partial ordering of the e _g orbitals of cobalt. The accompanying change in the interatomic distances and valence angles give rise to an anomaly in the temperature dependence of the magnetic susceptibility at T ≈ 120 K. The ordered magnetic moment μ_Co ≈ 2μ_B corresponds to the assumption of the intermediate spin state of Co³⁺ ions and the mixture of low- and intermediate-spin states of Co⁴⁺ ions.     

Search for ν<Subscript>μ</Subscript> → ν<Subscript>τ</Subscript> oscillations in appearance mode in the OPERA experiment

The OPERA experiment at the underground Gran Sasso Laboratory (LNGS) has to perform the first detection of neutrino oscillations in appearance mode through the direct observation of ν_μ → ν_τ. The apparatus consists of a lead/emulsion-film target complemented by electronic detectors. It is placed in the high-energy, long-baseline CERN neutrino beam (CNGS) 730 km away from the neutrino source. Runs with CNGS neutrinos were successfully carried out in 2008–2009 with the first candidate event ν_μ → gv_τ recently detected.     

Field-induced valence transition in EuPtP<Subscript>1−x</Subscript>As<Subscript>x</Subscript>

The ternary compound EuPtP exhibits two valence transitions at T ₁ = 235 K and T ₂ = 190 K. In order to examine a field-induced valence transition of Eu, we synthesized EuPtP_1−x As _x compounds with 0.05 ≤ x ≤ 0.5 and studied the magnetic and valence behavior. The substitution of As for P increases the lattice volume linearly and decreases both valence transition temperatures, T ₁ and T ₂, in contrast to the behavior under external pressures. The magnetization process in a pulsed magnetic field revealed that EuPtP_0.5As_0.5 exhibits an onset of metamagnetic transition above 50 T with a large hysteresis, which evidences a first-order field-induced valence transition. The analysis of the magnetization curves of x = 0.5 at various temperatures has demonstrated that the field-induced transition is essentially the same as the transition induced by temperature at T ₁.     

Remote substituent effects on homolytic Fe?C bond energies of p‐G‐C6H4CH2Fe(CO)2(η5‐C5H5) and p‐G‐C6H4(H)(CN)CFe(CO)2(η5‐C5H5) studied by Hartree–Fock and density functional theory methods

In general, both stoichiometric and catalytic reactions of organometallic complexes involve breaking and forming metal–ligand bonds. Therefore, an evaluation of the thermodynamics of such reactions requires the knowledge of metal–ligand bond energies (BDEs). The homolytic Fe? C bond dissociation energies [i.e., ΔH_homo(Fe? C)s] of 12 para‐substituted benzyldicarbonyl(η⁵‐cyclopentadienyl)iron, p‐G‐C₆H₄CH₂Fp [1,G = NO₂, CN, COMe, CO₂Me, CF₃, Br, Cl, F, H, Me, MeO, NMe₂; Fp = (η⁵‐C₅H₅)(CO)₂Fe] and 12 para‐substituted α‐cyanobenzyldicarbonyl (η⁵‐cyclopentadienyl)iron, p‐G‐PANFp [2,PAN = C₆H₄CH(CN)] were studied using Hartree–Fock (HF) and density functional theory (DFT) methods with large basis sets. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of ΔH_homo(Fe? C)s. The B3LYP method satisfactorily predicts the α and remote substituent effects on ΔH_homo(Fe? C)s [ΔΔH_homo(Fe? C)s]. The fair correlations [r = 0.97 (g, 1), 0.99(g, 2)] of ΔΔH_homo(Fe? C)s of series 1 and 2 with the substituent σ constants imply that the para substituent effects on ΔH_homo(Fe? C)s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. The molecule stabilization effects (MEs) causes that not only the magnitude of ΔΔH_homo(Fe? C)s(1) varies significantly but also the direction changes from S‐pattern to O‐pattern. ΔΔH_homo(Fe? C)s(2) were found to conform to the Capto‐dative Principle. The detailed knowledge of the factors that determine the Fp? C bond strengths would greatly aid in understanding reactivity patterns in many processes. Copyright © 2010 John Wiley & Sons, Ltd.     

Electronic excitation energies in TiO<Subscript>2</Subscript> in the fluorite phase

The ab initio pseudopotential method within the generalized gradient approximation (GGA) and quasiparticle approximation has been used to investigate the electronic properties of titanium dioxide in the rutile, anatase, and fluorite structures, respectively. Here we present the GW approximation for the electronic self-energy, which allows to calculate excited-state properties, especially electronic band structures. For this calculation, good agreement with the experimental results for the minimum band gaps in rutile and anatase phase is obtained. In the fluorite phase we predict that titanium dioxide will be an indirect (Γ to X) wide band-gap semiconductor (2.367 or 2.369 eV) and the properties remain to be confirmed by experiment.     

“Forbidden” reflections in resonant diffraction of synchrotron radiation in yttrium aluminum garnet Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>

The purely resonant Bragg reflections (13, 13, 0) and (14, 0, 0) in yttrium aluminum garnet Y₃Al₅O₁₂ at energies near the K absorption edge of yttrium have been studied experimentally and theoretically. The anisotropic tensor atomic factor of yttrium corresponding to dipole-dipole resonance transitions depends on three independent parameters changing with energy. The intensities of the reflections (14, 0, 0) and (13, 13, 0) are shown to depend on the parameter difference f ₁(E) − f ₂(E) and the parameter f ₃(E), respectively, which are attributable to distortions of the wave functions of the excited atoms and change greatly with photon energy E. Studying various reflections has allowed one to determine the various components of the tensor atomic factor and to compare them with the results of numerical calculations.     

Approximate wø ∽ Ωø Relations in Quintessence Models

Quintessence field is a widely-studied candidate of dark energy. There is ``tracker solution' in quintessence models, in which evolution of the field ø at present times is not sensitive to its initial conditions. When the energy density of dark energy is neglectable (Ω<sub>ø</sub><< 1), evolution of the tracker solutioncan be well analysed from ``tracker equation'. In this paper, we try tostudy evolution of the quintessence field from ``full tracker equation',which is valid for all spans of Ω<sub>ø.</sub> We get stable fixed points of w<sub>ø</sub> and Ω<sub>ø</sub> (noted as \hat{w}<sub>ø</sub> and \hat{Ω}<sub>ø</sub>) from the ``full tracker equation', i.e., w_ø and Ω_ø will always approach \hat{w}_ø and \hat{Ω}_ø respectively. Since \hat{w}_ø and \hat{Ω}_ø are analytic functions of ø, analytic relation of \hat{w}_ø ~ \hat{Ω}_ø can be obtained, which is a good approximation for the w_ø ~ Ω_ø relation and can be obtained for the most type of quintessence potentials. By using this approximation, we find that inequalities \hat{w}_ø < w_ø and \hat{Ω}_ø < Ω_ø are statisfied if the w_ø (or \hat{w}_ø) decreases with time. In this way, the potential U(ø) can be constrained directly from observations, by no need of solving the equations of motion numerically.