Fracture of silicate glasses: ductile or brittle?

Atomic force microscopy is used to investigate the possibility of cavity formation during crack growth in silicate glasses. Matching areas on both fracture surfaces were mapped and then compared. For silica glass, and soda-lime-silicate glass, the fracture surfaces matched to a resolution of better than 0.3 nm normal to the surface and 5 nm parallel to the surface. We could find no evidence for cavity formation in our study and suggest that completely brittle fracture occurs in glass.     

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.     

Assignment of pre‐edge peaks in K‐edge x‐ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole?

The characteristics of pre‐edge peaks in K‐edge x‐ray absorption near edge structure (XANES) spectra of 3d transition metals were reviewed from viewpoints of the selection rule, coordination number, number of d‐electrons, and symmetry of the coordination sphere. The contribution of the electric dipole and quadrupole transition to the peaks was discussed on the basis of the group theory, polarized spectra, and theoretical calculations. The pre‐edge peak intensity for T_d symmetry is larger than those for O_h symmetry for all 3d elements. The intense pre‐edge peak for tetrahedral species of 3d transition metals is not due to 1s–3d transition, but transition to the p component in d–p hybridized orbital. The mixing of metal 4p orbitals with the 3d orbitals depends strongly on the coordination symmetry, and the possibility is predictable by group theory. The transition of 1s electron to d orbitals is electric quadrupole component in any of the symmetries. The d–p hybridization does not occur with regular octahedral symmetry, and the weak pre‐edge peak consists of 1s–3d electric quadrupole transition. The pre‐edge peak intensity for a compound with a tetrahedral center changes as a function of the number of 3d electrons regardless of the kind of element; it is maximized at d⁰ and gradually decreases to zero at d¹⁰. The features of pre‐edge peaks in K‐edge XANES spectra for 4d elements and the L₁‐edge for 5d elements are analogous with those for 3d elements, but the pre‐edge peak is broadened due to the wide natural width of the core level. Copyright © 2008 John Wiley & Sons, Ltd.     

The Weinberg‐Salam Model of Electroweak Interactions: Ingenious Discovery or Lucky Hunch?

This contribution looks back at the papers published fifty years ago by Abdus Salam and Steven Weinberg, which are today regarded as marking the coming‐to‐be of the Weinberg‐Salam model of electroweak interactions. Despite their present fame, at the time of their publication the papers went largely unnoticed. Reconstructing the historical context from which they emerged will show how, against the traditional image of theoretical physicists as “lone geniuses,” the Weinberg‐Salam model actually came to be thanks to the interplay of many different actors and ideas.     

The local adsorption site of methylthiolate on Au(1 1 1): Bridge or atop?

Measurements of the local adsorption geometry of the S head-group atom in the Au(1 1 1)(√3 × √3)R30°-CH₃S surface have been made using normal incidence X-ray standing waves (NIXSW) and S 1s scanned-energy mode photoelectron diffraction on the same surface preparations. The results confirm that the local adsorption site is atop an Au atom in a bulk-continuation site with a S-Au bondlength of 2.42 ± 0.02 Å, and that there can be no significant fraction of coadsorbed bridging species as recently proposed in a combined molecular dynamics/experimental study by Mazzarello et al. [R. Mazzarello, A. Cossaro, A. Verdini, R. Rousseau, L. Casalis, M.F. Danisman, L. Floreano, S. Scandolo, A. Morgante, G. Scoles, Phys. Rev. Lett. 98 (2007) 016102]. The results do not, however, clearly distinguish the different local reconstruction (adatom) models proposed for this surface.     

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.     

Can tetra‐tert‐butylethylene be formed by ion–ion recombination or ion–molecule reaction of two di‐tert‐butylcarbene units?—a DFT study

The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C? (CH₃)₃ bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH₃ and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C? H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH₃ migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd.     

Self‐trapped N?H vibrational states in the polymorphs of glycine,L‐ and DL‐alanine

The polarized Raman spectra of the oriented single crystals of L ‐ and DL ‐alanine, α‐, β‐ and γ‐polymorphs of glycine have been studied at 3–300 K. Regularly spaced band packets have been observed in the spectral range of 2500–3000 cm⁻¹, with intensity decreasing noticeably on heating. These band packets were interpreted as the manifestations of the existence of N H self‐trapped states in these systems at low temperatures. The analysis of the polarized spectra has shown that the self‐trapping is observed exclusively for the NH stretching vibration of the amino groups, which is related to the NH···O hydrogen bonds along the head‐to‐tail chains of zwitterions in the crystal structures. The wavenumber of this NH stretching vibration, however, was proposed to depend not solely on the length of this NH···O hydrogen bond, but also on the lengths of all the other NH···O hydrogen bonds formed by the NH₃⁺ and the COO⁻ groups in the structure linking the head‐to‐tail chains with each other. The arguments in favor of the hypothesis that the self‐trapping in these systems can be mediated by zero‐point quantum motions, and not by lattice phonons, are considered. The unusually low wavenumber (2500 cm⁻¹) observed for the NH stretching vibration and indicating at the formation of a very strong NH···O bond is interpreted based on considering the effect of the crystalline environment on the formation and properties of the NH···O bonds in the head‐to‐tail chains of amino acid zwitterions. The results are interesting for understanding the factors determining the dynamics and structural instability of crystalline amino acids and also for biophysical chemistry, as the hydrogen bonded chains formed by amino acid zwitterions in the crystals can mimic the peptide chains. Copyright © 2009 John Wiley & Sons, Ltd.     

Electron transfer within 1,3‐dinitrobenzene radical anions: electron hopping or superexchange?

The intramolecular electron transfer on several 1,3‐dinitrobenzene radical anions with different substituents on position 5 was studied by electron paramagnetic resonance and optical spectroscopies in MeCN. The radical anions are all charge‐localized mixed valence species, as is common for meta‐substituted dinitrobenzenes. Rate constants for the electron transfer reaction were obtained by the Marcus–Hush analysis of the intervalence optical bands assuming quartic‐augmented energy surfaces and solvent‐controlled dynamics. These calculated rate constants match quite well the experimental ones obtained by simulation of the electron paramagnetic resonance spectra, which rules out bridge‐reduced states as intermediates in the reaction path and confirms the superexchange mechanism. Copyright © 2012 John Wiley & Sons, Ltd.     

Consonant identification under maskers with sinusoidal modulation: masking release or modulation interference?

The present study investigated the effect of envelope modulations in a background masker on consonant recognition by normal hearing listeners. It is well known that listeners understand speech better under a temporally modulated masker than under a steady masker at the same level, due to masking release. The possibility of an opposite phenomenon, modulation interference, whereby speech recognition could be degraded by a modulated masker due to interference with auditory processing of the speech envelope, was hypothesized and tested under various speech and masker conditions. It was of interest whether modulation interference for speech perception, if it were observed, could be predicted by modulation masking, as found in psychoacoustic studies using nonspeech stimuli. Results revealed that masking release measurably occurred under a variety of conditions, especially when the speech signal maintained a high degree of redundancy across several frequency bands. Modulation interference was also clearly observed under several circumstances when the speech signal did not contain a high redundancy. However, the effect of modulation interference did not follow the expected pattern from psychoacoustic modulation masking results. In conclusion, (1) both factors, modulation interference and masking release, should be accounted for whenever a background masker contains temporal fluctuations, and (2) caution needs to be taken when psychoacoustic theory on modulation masking is applied to speech recognition.     

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.     

Structure identification and site preference of Ta and Cd in Ti–Pd alloys: A first-principle study

By means of a density functional theory approach, we studied the electric field gradients (EFG) in Ta and Cd-doped Ti–Pd intermetallics. Our results confirmed the previous experimental findings that the TiPd₂ low-temperature structure is orthorhombic and established that Ta substitutes for Ti in this structure. The temperature increase above 650 K changes the Ta impurity position in the lattice. Similar changes for the Cd doped system were not confirmed, as Cd is most likely to occupy Pd lattice sites in both low and high-temperature phases. In the case of TiPd, our calculations suggested that Ta substitutes for Ti in the low-temperature phase, while Cd probably can substitute on both Ti and Pd crystallographic sites.     

Dynamic surface tension of complex fluid-fluid interfaces: A useful concept, or not?

Dilatational moduli are typically determined by subjecting interfaces to oscillatory area deformations, and are often defined in terms of the difference between the dynamic or transient surface tension of the interface (the surface tension in its deformed state), and the surface tension of the interface in its non-deformed state. Here we will discuss the usefulness of the dynamic surface tension concept in the characterization of dilatational properties of complex fluid-fluid interfaces. Complex fluid-fluid interfaces are interfaces stabilized by components which form mesophases (two-dimensionional gels, glasses, or (liquid) crystalline phases), as a result of in-plane interactions between the components. We will show that for such interfaces dilatational properties are not exclusively determined by the exchange of surface active components between interface and adjoining bulk phases, but also by in-plane viscoelastic stresses. The separation of these contributions remains a challenging problem which remains to be solved.     

PIXE–RBS survey of a Meissen porcelain snuff box: first version or not?

Non‐destructive materials analysis provided essential knowledge for deciding on the complete authenticity of a unique work of art made from porcelain, rich of delicate painting. The combination of ion‐beam based methods proton‐induced X‐ray emission (PIXE) and Rutherford‐backscattering spectrometry (RBS) was able to make simultaneously available both bulk composition and surface characterization. Potential differences in glazing and painting materials were verified when examining the base body and the lid of the box. In particular, RBS from Pb atoms in the near‐surface depth region could identify lead‐glazing for the shaded porcelain of the bottom. The chemical composition of the brilliant glaze of the lid was proved by PIXE to conform to the typical Meissen recipe. Consequently, a later completed or restored object was deduced. Copyright © 2012 John Wiley & Sons, Ltd.     

Involvement of weak C?H···X hydrogen bonds in metal‐to‐semiconductor regime change in one‐dimensional organic conductors (o‐DMTTF)2X (X = Cl,Br, and I): combined IR and Raman studies

We report on the infrared (IR) and Raman studies of the three isostructural quasi‐one‐dimensional cation radical salts of 3,4‐dimethyl‐tetrathiafulvalene (o‐DMTTF)₂X (X = Cl, Br, and I), which all exhibit metallic properties at room temperature and undergo transitions to a semiconducting state in two steps: a soft metal‐to‐semiconductor regime change in the temperature region T_ρ = 5–200 K and then a sharp phase transition at about T_MI = 50 K. Polarized IR reflectance spectra (700–16 000 cm⁻¹) and Raman spectra (50–3500 cm⁻¹, excitation λ = 632.8 nm) of single crystals were measured as a function of temperature (T = 5–300 K) to assess the eventual formation of a charge‐ordered state below 50 K. Additionally, the temperature dependence of the IR absorption spectra of powdered crystals in KBr discs was also studied. The Raman spectra and especially the bands related to the CC stretching vibration of o‐DMTTF provide unambiguous evidence of uniform charge distribution on o‐DMTTF down to the lowest temperatures, without any modification below 50 K. However, the temperature dependence of Raman spectra indicates a regime change below about 200 K. Temperature dependence of both electronic dispersion and vibrational features observed in the IR spectra also clearly confirms the regime change below about 200 K and shows the involvement of C H···X hydrogen bonds in the electronic localization; some spectral changes can be also related with the phase transition at 50 K. Additionally, using density functional theory methods, the normal vibrational modes of the neutral o‐DMTTF⁰ and cationic o‐DMTTF⁺ species, as well as their theoretical IR and Raman spectra, were calculated. The theoretical data were compared with the experimental IR and Raman spectra of neutral o‐DMTTF molecule. Copyright © 2011 John Wiley & Sons, Ltd.     

Saturation of nuclear partons: Fermi statistics or nuclear opacity?

We derive the two-plateau momentum distribution of final state (FS) quarks produced in deep inelastic scattering (DIS) off nuclei in the saturation regime. The diffractive plateau, which dominates for small p, measures precisely the momentum distribution of quarks in the beam photon; the role of the nucleus is simply to provide an opacity. The plateau for truly inelastic DIS exhibits a substantial nuclear broadening of the FS momentum distribution. We discuss the relationship between the FS quark densities and the properly defined initial state (IS) nuclear quark densities. The Weizsäcker-Williams glue of a nucleus exhibits a substantial nuclear dilution, still soft IS nuclear sea saturates because of the anti-collinear splitting of gluons into sea quarks.     

Forecasting volatility of fuel oil futures in China: GARCH-type,SV or realized volatility models?

In most previous works on forecasting oil market volatility, squared daily returns were taken as the proxy of unobserved actual volatility. However, as demonstrated by Andersen and Bollerslev (1998) [22], this proxy with too high measurement noise could be perfectly outperformed by a so-called realized volatility (RV) measure calculated by the cumulative sum of squared intraday returns. With this motivation, we further extend earlier works by employing intraday high-frequency data to compare the performance of three typical volatility models in the daily out-of-sample volatility forecasting of fuel oil futures on the Shanghai Futures Exchange (SHFE): the GARCH-type, stochastic volatility (SV) and realized volatility models. By taking RV as the proxy of actual daily volatility and then computing forecasting errors, we find that the realized volatility model based on intraday high-frequency data produces significantly more accurate volatility forecasts than the GARCH-type and SV models based on daily returns. Furthermore, the SV model outperforms many linear and nonlinear GARCH-type models that capture long-memory volatility and/or the asymmetric leverage effect in volatility. These results also prove that abundant volatility information is available in intraday high-frequency data, and can be used to construct more accurate oil volatility forecasting models.     

“Could charm (& τ ) transitions be the ‘poor princess’ providing a deeper understanding of fundamental dynamics ?” or: “Finding novel forces”

We know that our Universe is composed of only ～4.5% “known” matter; therefore, our understanding is incomplete. This can be seen directly in the case of neutrino oscillations (without even considering potential other universes). Charm quarks have had considerable impact on our understanding of known matter, and quantum chromodynamics (QCD) is the only local quantum field theory to describe strong forces. It is possible to learn novel lessons concerning strong dynamics by measuring rates around the thresholds of [QˉQ] states with Q = b, c. Furthermore, these states provide us with gateways towards new dynamics (ND), where we must transition from “accuracy” to “precision” eras. Finally, we can make connections with τ transitions and, perhaps, with dark matter. Charm dynamics acts as a bridge between the worlds of light- and heavy-flavor hadrons (namely, beauty hadrons), and finding regional asymmetries in many-body final states may prove to be a “game changer”. There are several different approaches to achieving these goals: for example, experiments such as the Super Tau-Charm Factory, Super Beauty Factory, and the Super Z⁰ Factory act as gatekeepers – and deeper thinking regarding symmetries.