The pair-production channel in atomic processes

Assisted by the creation of electron–positron pairs, new channels for ionization, excitation, and charge transfer open in atomic collisions when the energy is raised to relativistic values. At extreme energies these pair-production channels usually dominate the “traditional” contributions to cross sections that involve only “positive-energy” electrons. An extensive body of theoretical and experimental work has been performed over the last two decades to investigate charge-changing processes catalyzed by pair production in relativistic heavy ion collisions. We review some of these studies.     

The Correct Meaning of “Coating Efficiency” vs. the “Utilization of Theoretical Efficiency”

The correct meaning of the the term “utilization of the theoretical efficiency” vs. the “coating efficiency” is explained.     

Expanding the Scope of Arylsulfonylacetylenes as Alkynylating Reagents and Mechanistic Insights in the Formation of Csp2?Csp and Csp3?Csp Bonds from Organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected “anti‐Michael” reactions observed for substituted sulfonylacetylenes.     

“Grafting through” polymerization involving surface-bound monomers

“Grafting through” polymerization represents copolymerization of free monomers in solution and polymerizable units bound to a substrate. Free polymer chains are formed initially in solution and can incorporate the surface-bound monomers, and thereby, get covalently bonded to the surface during the polymerization process. As more growing chains attach to the surface-bound monomers, an immobilized polymer layer is formed on the surface. We use a combination of computer simulation and experiments to comprehend this process for monomers bound to a flat impenetrable substrate. We concentrate specifically on addressing the effect of spatial density of the surface-bound monomers on the formation of the surface-attached polymers. We employ a lattice-based Monte Carlo model utilizing the bond fluctuation model scheme to provide molecular-level insight into the grafting process. For experimental validation, we create gradients of density of bound methacrylate units on flat silicon wafers using organosilane chemistry and carry out “grafting through” free radical polymerization initiated in bulk. We report that the proximity of the surface-bound polymerizable units promotes the “grafting through” process but prevents more free growing chains to “graft through'' the polymerizable units. The “grafting through” process is self-limiting in nature and does not affect the overall density of the surface-bound polymer layer, except in case of the highest theoretical packing density of surface-bound monomers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 263–274     

Hydration of GABA and of the GABA·ZN2+ complex: A Monte Carlo simulation study

With empirical and theoretical atom–atom potentials the GABA·nH₂O, n = 25, 192 and GABA·Zn²⁺ · nH₂O, n = 25, 50, 100 complexes are simulated at 298.15 K by the Monte Carlo technique. The results show that the carboxyl group of GABA coordinates six water molecules. Two geometries of the GABA·Zn²⁺ complex, corresponding to the “direct” and “through-water” interaction of Zn²⁺ with the carboxyl group of GABA were found. For the latter interaction a GABA·Zn²⁺ · 6H₂O complex was found whereas the hydration of the former interaction leads to a GABA·Zn²⁺ · 5H₂O complex. Here the carboxyl group of GABA displaces only one water molecule in the first hydration shell of Zn²⁺. Energetically the “direct” and “through-water” geometries seem to be competitive, the former being slightly favored.     

“元素化学实验”中的“异常”现象(一)--Mn元素化学实验中的“异常”现象及其探析

大一学生在“元素化学实验”教学过程中,对反应条件如温度、催化剂、酸度、浓度或试剂用量等因素的影响考虑不周,可能出现某些实验现象和预想的或理论分析的结果不一致的“异常”现象。本文就学生在Mn元素化学实验过程中遇到的一些“异常”现象进行分析和总结,借助生动直观的演示实验,引导学生探究“异常”现象产生的可能原因和直观认识反应条件对反应结果的影响,培养学生的观察、分析、判断、归纳、推理和解决实际问题的能力。     

“元素化学实验”中的“异常”现象(一)--Mn元素化学实验中的“异常”现象及其探析

大一学生在“元素化学实验”教学过程中,对反应条件如温度、催化剂、酸度、浓度或试剂用量等因素的影响考虑不周,可能出现某些实验现象和预想的或理论分析的结果不一致的“异常”现象。本文就学生在Mn元素化学实验过程中遇到的一些“异常”现象进行分析和总结,借助生动直观的演示实验,引导学生探究“异常”现象产生的可能原因和直观认识反应条件对反应结果的影响,培养学生的观察、分析、判断、归纳、推理和解决实际问题的能力。     

Quantitative Evaluation of Infrared Absorbance Spectra – Lorentz Profile versus Lorentz Oscillator

We present the theoretical basis for a profound upgrade of the method of absorbance band fitting (“band deconvolution”), which requires only minute changes in the code of corresponding spectrometer software. This upgrade is based on a (re-)connection of the damped harmonic oscillator model (“Lorentz oscillator”) and the Lorentz profile used for band fitting. Based on this reconnection, we provide a proper extension to multiple oscillators. As a result, band fitting allows directly obtaining all oscillator parameters with very good accuracy, at least for the not too strong oscillators present in organic and biological matter. Accordingly, this could be the initial spark to open the way to a long-awaited paradigm shift in infrared spectroscopy: Away from a mere oscillator position-based, towards an also intensity-based quantitative interpretation of spectra. As an extra, absorbance band fitting (“Poor Man's Dispersion Analysis”), allows to obtain the index of refraction function in one go.     

Anti‐Electrostatic Hydrogen Bonds

Ab initio and hybrid density functional techniques were employed to characterize a surprising new class of H‐bonded complexes between ions of like charge. Representative H‐bonded complexes of both anion–anion and cation–cation type exhibit appreciable kinetic stability and the characteristic theoretical, structural, and spectroscopic signatures of hydrogen bonding, despite the powerful opposition of Coulomb electrostatic forces. All such “anti‐electrostatic” H‐bond (AEHB) species confirm the dominance of resonance‐type covalency (“charge transfer”) interactions over the inessential (secondary or opposing) “ionic” or “dipole–dipole” forces that are often presumed to be essential for numerical modeling or conceptual explanation of the H‐bonding phenomenon.     

Valence-Shell Electron-Pair Repulsion Theory Revisited: An Explanation for Core Polarization

Valence-shell electron-pair repulsion (VSEPR) theory constitutes one of the pillars of theoretical predictive chemistry. It was proposed even before the advent of the concept of “spin”, and it is still a very useful tool in chemistry. In this article we propose an extension of VSEPR theory to understand the core structure and predict core polarization in the main-group elements. We show from first principles (Electron Localization Function analysis) how the inner- and outer-core shells are organized. In particular, electrons in these regions are structured following the shape of the dual polyhedron of the valence shell (3^rd period) or the equivalent polyhedron (4^th and 5^th periods). We interpret these results in terms of “hard” and “soft” core character. All the studied systems follow this trend, providing a framework for predicting electron distribution in the core. We also show that lone pairs behave as “standard ligands” in terms of core polarization. The predictive character of the model was tested by proposing the core polarization in different systems not included in the original set (such as XeF₄ and [Fe(CN)₆]³⁻) and checking the hypothesis by means of a posteriori calculations. From the experimental point of view, the extension of VSEPR to the core region has consequences for current crystallography research. In particular, it explains the core polarization revealed by high resolution X-ray experiments.     

A comparative account of properties of novel unsaturated polyesters synthesized by different polyesterification processes

NUP-7(II) has already proved its potential for inhibition of CMDB propellants. NUP-7(I), NUP-7(II), and NUP-7(III) have been synthesized by “one-step,” “two-step,” and “three-step” processes of polyesterification and their various characteristics have been studied and discussed in terms of theoretical considerations. NUP-7(III) possesses better elongation and higher chemical resistance (low nitroglycerine absorption)—two contradictory characteristics reported in the case of most of the polymeric materials. It therefore will have added advantages over NUP-7(II) for military as well as civil applications.     

Adsorption Sequence of Multifunctional Groups: A Study on the Reaction Pathway and the Adsorption Structure of Homocysteine on the Ge(100) Surface

We investigated the adsorption mechanism of homocysteine (HS? CH₂? CH₂? CH(NH₂)? COOH) on the Ge(100) surface along with its electronic structures and adsorption geometries to determine the sequence of adsorption of this amino acid′s functional groups using core‐level photoemission spectroscopy (CLPES) in conjunction with density functional theory (DFT) calculations. We found that the “SH‐dissociated OH‐dissociated N‐dative‐bonded structure” and the “SH‐dissociated OH‐dissociation‐bonded structure” were preferred at a monolayer (ML) coverage of 0.30 (lower coverage) and 0.60 (higher coverage), respectively. The “SH‐dissociated OH‐dissociated N‐dative‐bonded structure” was the most stable structure. Moreover, we systematically confirmed the sequence of adsorption of the functional groups of the homocysteine molecule on the Ge(100) surface, which is thiol group (? SH), carboxyl group (? COOH), and amine group (? NH₂).     

Poly(N‐isopropylacrylamide) Phase Diagrams: Fifty Years of Research

In 1968, Heskins and Guillet published the first systematic study of the phase diagram of poly(N‐isopropylacrylamide) (PNIPAM), at the time a “young polymer” first synthesized in 1956. Since then, PNIPAM became the leading member of the growing families of thermoresponsive polymers and of stimuli‐responsive, “smart” polymers in general. Its thermal response is unanimously attributed to its phase behavior. Yet, in spite of 50 years of research, a coherent quantitative picture remains elusive. In this Review we survey the reported phase diagrams, discuss the differences and comment on theoretical ideas regarding their possible origins. We aim to alert the PNIPAM community to open questions in this reputably mature domain.     

“Anti-electrostatic” Halogen Bonding between Ions of Like Charge

Halogen bonding occurs between molecules featuring Lewis acidic halogen substituents and Lewis bases. It is often rationalized as a predominantly electrostatic interaction and thus interactions between ions of like charge (e. g., of anionic halogen bond donors with halides) seem counter-intuitive. Herein, we provide an overview on such complexes. First, theoretical studies are described and their findings are compared. Next, experimental evidences are presented in the form of crystal structure database analyses, recent examples of strong “anti-electrostatic” halogen bonding in crystals, and the observation of such interactions also in solution. We then compare these complexes to select examples of “counter-intuitive” adducts formed by other interactions, like hydrogen bonding. Finally, we comment on key differences between charge-transfer and electrostatic polarization.     

On the choice of gauge for approximate quantum mechanical wavefunctions

Since gauge invariance cannot be preserved for approximate wavefunctions it is suggested that one use this freedom inherent in the theoretical treatment to pick the “best” gauge for expressing the operators in, with respect to the particular basis set of the calculation. It is argued that the “best” gauge is that which minimizes the variance of the operator under consideration for the basis set.     

Time‐of‐flight mass spectrometry depth profiling of sodium‐implanted polyethylene terephthalate

Depth profiling analysis of sodium (Na)‐implanted polyethylene terephthalate was performed by using time‐of‐flight secondary ion mass spectrometry in the cesium‐attachment regime. A radical redistribution of the main element due to diffusion and escape of some elements, such as oxygen and hydrogen, and carbonization of a top 550 nm layer were observed. The depth distribution of the implanted sodium was found to be radically different from the “theoretical” distribution calculated by using the Monte Carlo simulation method (TRIM code). We conclude that it is possible to perform an effective depth profiling analysis of an implanted polymer in the “standard” secondary ion mass spectrometry regime without using a big cluster primary ion beam.     

Bubble Solution Description by Non-Extensive Thermodynamics: Pressure Effect

We showed in this study that nanobubble solutions should not be considered as the simple juxtaposition of autonomous phases (a solution and bubbles) but as particular entities, that is, “supersaturated solutions” where gas is simultaneously in two forms in permanent exchange. Gibbs′ extensive thermodynamics cannot claim to describe legitimately their behavior. In this work, we showed how the use of the non-extensive thermodynamics allows describing the physicochemical properties of such media, some of which are counter-intuitive. Thus, an increase in pressure can result in an increase in the bubble size, contrary to what is provided by Boyle-Mariotte's law. The theoretical relationships proposed in this work constitute another approach to bubble solutions, which considers the non-autonomous nature of the components of supersaturated gas solutions and their “non-extensive” nature.