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.     

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.     

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.     

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.     

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.     

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.     

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.     

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)     

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.     

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.     

Why the ΔνCH blue shift is larger in chloral than in dichloroacetyl chloride dimers?

Raman spectra of the Cl₃CCHO/CCl₄ and Cl₃CCHO/C₆D₁₂ binary systems were recorded as a function of the mole fraction. Features originating from self‐aggregates of chloral (trichloroethanal, trichloroacetaldehyde—TCAA) molecules were detected in different spectral regions. The most pronounced changes were observed in the vicinity of the ν(CO) and ν(C H) stretching vibration bands. Using two‐dimensional correlation spectroscopy (2D‐COS), evolving‐factor analysis (EFA) and multivariate curve resolution (MCR), dimer bands were identified, and their positions were determined. The ν(C H) stretching vibration band in dimers was blue‐shifted by nearly 18 cm⁻¹, whereas the ν(CO) dimer band was red‐shifted by more than 5 cm⁻¹. For these bands, the observed shifts were accompanied by an almost twofold change in the bandwidth, from approximately 19 and 6 cm⁻¹ for dilute solutions (x = 0.05) to 36.6 and 11.5 cm⁻¹, respectively, in pure TCAA. The formation of dimers was confirmed by multivariate analysis of the Raman spectra of chloral recorded as a function of temperature. Analogous analysis of dichloroacetyl chloride (DCAC) spectra gave an 8.9 cm⁻¹ blue shift for the ν(C H) vibration band and − 5.5/− 10.1 cm⁻¹ shifts for the ν(CO) stretching vibrations of the two conformers present. To facilitate the interpretation of experimental findings, the optimized geometries and vibrational wavenumbers of the Cl₃CCHO/HCl₂CCClO molecules and (Cl₃CCHO)₂/(HCl₂CCClO)₂ dimers were calculated at the B3LYP/6‐311 + + G(3df,3pd) level. 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.     

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.     

What are the correct L‐subshell photoionization cross sections for quantitative X‐ray spectroscopy?

For fundamental parameter‐based, quantitative X‐ray fluorescence, X‐ray photoelectron spectroscopy or Auger electron spectroscopy, it is crucial to accurately know the photoionization cross sections (PCS). This atomic probability to absorb the exciting photon and eject a photoelectron, in general, followed by a subsequent decay resulting in the emission of a fluorescence photon or an Auger electron, strongly depends on the electron configuration and photon energy. Two contrary models for the photon energy dependence of the L‐subshell PCS, or the 2s, 2p ½ and 2p 3/2; energy levels, respectively, exist in the literature, and an experimental verification was not available until recently. In this work, the two models for calculating the PCS are discussed, and their influence on quantitative experiments is demonstrated by means of the fluorescence production cross sections for the three L shells. Depending on the excitation conditions, these fluorescence production cross sections and, thus, the derived quantitative results can differ significantly if the wrong PCS model is employed. Copyright © 2016 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.     

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.     

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.     

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.