A theoretical study for the band gap energies of the most common silica polymorphs

Although numerous theoretical studies are available for the band gap energies of distinct silica (SiO₂) polymorphs, some of the calculated results of these former studies still remain inconsistent and mostly disagree with the experimental data of the investigated polymorphs. To obtain more reasonable results, we have focused on the band gap energies of eleven different and more common silica polymorphs in this research by employing the self consistent charge (SCC) variant of the density functional based tight binding (DFTB) method. The surveyed eleven common silica polymorphs in this study are namely: α-quartz, β-quartz, α-tridymite, β-tridymite, α-cristobalite, β-cristobalite, α-moganite, β-moganite, stishovite, coesite, and keatite Our obtained band gap energy results for α-quartz and stishovite are undoubtedly reasonable when compared with the existing experimental data of these polymorphs. As well, the maximum band gap energy is found to be as 9.70 eV for the β-moganite polymorph, and the minimum band gap energy appears as 7.62 eV for the stishovite polymorph. Overall, the presently obtained results for the energy band gap of the considered silica polymorphs are satisfactory, and some of them are still waiting further experimental confirmation.     

Control of morphology for energy dissipation in carbon nanotube forests

This study focuses on the effect of carbon precursor on the carbon nanotube (CNT) morphology and energy dissipation. Benzene, toluene, and m-xylene were used as carbon precursors for the synthesis of CNT forests following a chemical vapor deposition process. The results indicate that substituents on the benzene ring increase entanglement in the CNT forests. The absorbed energy was slightly greater for CNT forests synthesized using m-xylene than for toluene, but was much smaller for benzene. When compressed to a strain of 0.67, the toluene CNTs absorbed more energy than the m-xylene CNTs. The restitution was much higher for the forests synthesized with m-xylene than toluene while it further decreased for the forests made with benzene. A strong correlation is also observed between the average diameter of the CNTs and the number of methyl substituents on the benzene ring. The control of the entanglement of the CNT forests can potentially be used to design high energy absorbing composites for blast energy dissipation.     

并五苯同质异相体中分子间势能与能带计算

采用Born-Mayer-Haggins对势模型，分析了并五苯分子间势能及其相互作用. 用紧束缚模型计算了两种并五苯同质异相体结构的能带宽度. 计算带宽随温度升高减小8%—14%. 关键词： 并五苯 同质异相体 分子间势能 能带计算     

Amorphous,nanocrystalline and crystalline calcium carbonates in biological materials

Raman spectroscopy is a powerful tool in identifying different calcium carbonate polymorphs. Here, the method is applied to cultured pearls from freshwater (genus Hyriopsis) and marine bivalve species (Pinctada maxima) as well as to shells of Diplodon chilensis patagonicus bivalves. Raman spectra for vaterite, detected for the first time in an adult shell, and amorphous calcium carbonate (ACC) are discussed. Results for ACC are compared with those of synthetically produced ACC and with the Raman spectroscopic features of stable biogenic ACC from the crustacean Porcellio scaber. Decomposition of the most intense signal of all calcium carbonate polymorphs—the ν₁ symmetric stretching mode of the carbonate ion—leads to the identification of two polymorphs within the ACC areas: a mixure of an amorphous and a crystalline fraction. The amorphous phase is characterised by a broad peak in the region of the lattice modes, which is composed of two distinct lattice modes with very high full‐widths at half‐maximum (FWHMs). The FWHMs of most of the crystalline fractions (in the range of 6.3–10.7 cm⁻¹) are too high for well‐crystallised materials and support reports of nanocrystalline calcium carbonate polymorph clusters in ACC. Crystallinity indices of different samples are calculated and found to be useful to describe roughly the state of crystallisation in the ACC areas. Copyright © 2010 John Wiley & Sons, Ltd.     

Structural stability of nano-sized crystals of HMX: A molecular dynamics simulation study

The interaction potential energy and heat of sublimation of nanoparticles of HMX crystal polymorphs are studied by using molecular dynamics methods with a previously developed force field [Bedrov, et al., J. Comput.-Aided Mol. Des. 8 (2001) 77]. Molecular dynamics simulations of nanoparticles with 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100 molecules of HMX are carried out at 300 K. The intermolecular, intramolecular and total interaction energies per mole for the nanoparticles are calculated at 300 K. Then, we have calculated sublimation enthalpy of HMX crystal polymorphs with different sizes. For the all sizes, the β-HMX is found to be the most stable phase, due to having the least total interaction energy. Also, α-HMX is more stable than δ-HMX. An increase in the sublimation enthalpy with the size of the nanoparticle can be seen.     

Quantum effects in the structure of liquid benzene at room temperature

Structural differences between liquid light (protonated) benzene and heavy (deuterated) benzene at room temperature have been measured using high energy electromagnetic radiation scattering techniques. Intra- and intermolecular effects have been examined, and the main quantum contribution is shown to be intramolecular. This is in contrast to the quantum effects measured in liquid water at room temperature, which are primarily intermolecular.     

A theoretical examination of the chemisorption of benzene on Si(100)−(2 × 1)

A theoretical examination of the structure of the adsorbed state of benzene on the Si(100)-(2 × 1) surface is discussed. A number of potential candidate structures are examined. The local minimum in the total energy for each structure has been calculated with respect to variations in the atomic coordinates for the adsorbed benzene structure and the first four layers of the substrate. The preferred structure is the one with the lowest value for the total energy. This structure, in agreement with the experimental observations, describes a topology for the adsorbed benzene with no Si-H bonds and all the C-H bonds remaining intact. The benzene ring is oriented at an angle of 24° from the surface plane. Four of the carbon atoms are bonded to the silicon surface. Two silicon atoms are each bonded to two carbon atoms.     

Fully rotationally resolved ZEKE photoelectron spectroscopy of C6H6 and C6D6: photoionization dynamics and geometry of the benzene cation

A comprehensive set of spectra for the benzene cation and the perdeuterated benzene cation has been recorded with full rotational resolution using zero kinetic energy photoelectron spectroscopy (ZEKE) at high resolution (up to 0.2 cm^?1), using a slow-rising extraction pulse. With different rovibronic levels in the S₁ 6^l state as intermediate resonance, the rotational transitions to the vibronic ground state of the cation have been recorded using two-colour, two-photon resonance enhanced multiphoton ionization. A simple spectator model has been employed to simulate the intensities of the ZEKE transitions. By fitting the simulations to the recorded spectra, improved values for the rotational constants and the Coriolis coupling parameters of benzene and perdeuterated benzene have been obtained. The CC and CH bond lengths of the cation have been deduced. The spectator model is shown to be reliable despite the fact that no specific allowance is made for the effect of final state interactions on the signal intensity.     

Renormalization of molecular electronic levels at metal-molecule interfaces

The electronic structure of benzene on graphite (0001) is computed using the GW approximation for the electron self-energy. The benzene quasiparticle energy gap is predicted to be 7.2 eV on graphite, substantially reduced from its calculated gas-phase value of 10.5 eV. This decrease is caused by a change in electronic correlation energy, an effect completely absent from the corresponding Kohn-Sham gap. For weakly coupled molecules, this correlation energy change can be described as a surface polarization effect. A classical image potential model illustrates the impact for other conjugated molecules on graphite.     

浮选光度法测定痕量铜

根据 Cu(DDTC) 2 易浮选于苯中 ,建立了溶剂浮选测定铜的新光度法 ,本法灵敏度高 (ε=2 .9× 10 5L·mol-1·cm-1) ,精密度和选择性好 ,检出限低 ,适于天然水中痕量铜的测定     

Adsorption of magnetic transition metals on borophene: an ab initio study

We explore the doping strategy for adsorbing different metallic 3d transition-metal atoms (Fe, Co and Ni) on two different polymorphs of borophene monolayer: 2-Pmmn and 8-Pmmn borophene. Both have energy dispersion, with 2-Pmmn borophene being metallic in nature, and 8-Pmmn borophene being semi-metallic with a tilted Dirac cone like dispersion. Using density functional theory based calculations, we find the most suitable adsorption site for each adatom, and calculate the binding energy, binding energy per atom, charge transfer, density of states and magnetic moment of the resulting borophene-adatom system. We show that Ni is the most effective for electron doping for both the polymorphs. Additionally Fe is the most suitable to magnetically dope 8-Pmmn borophene, while Co is the best for magnetically doping 2-Pmmn borophene.     

Fluorescence Quenching Studies of 1,3‐Diphenyl Benzene

Fluorescence quenching of 1,3‐diphenyl benzene (m‐terphenyl) by carbon tetrachloride (CCl₄) at steady state in different solvents, namely n‐hexane, n‐heptane, cyclohexane, toluene, benzene acetonitrile, 1,4‐dioxane, and with a transient method in benzene has been done at room temperature to understand the role of quenching mechanisms. The Stern–Volmer plot was found to be linear for all the solvents studied. The probability of quenching per encounter p was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and lifetime measurements in benzene at different temperatures (30–60°C), it was shown that the phenomenon of quenching is generally governed by the well‐known Stern–Volmer (S‐V) plot. The activation energy E _a (E′_a) of quenching was determined using literature values of activation energy of diffusion E _d, and it was found to be greater than E _d, which confirms the fact that the quenching mechanism is not solely due to material diffusion but there is also contribution from activation energy.     

Regeneration of AG–AC beads for adsorption of monoaromatic compounds

This study investigates the possibility of monoaromatic compounds benzene and toluene adsorption onto alginate gel (AG–AC) beads with impregnated activated carbon and their regeneration possibility using ultrasound method. Kinetic adsorption tests showed that the AG–AC beads were capable of removing the organic compounds from either individual or mixed compound solutions. Removal ratio of the AG–AC beads was as high as that of free PAC powder for benzene and toluene. The removal was more efficient for toluene (97%) than for benzene (75%), and slightly decreased by 7% and 5% for toluene and benzene respectively even after 5 times regeneration. This indicates that the regeneration method utilizing ultrasound is very efficient for desorption of benzene and toluene from the AG–AC beads developed in this study.     

Raman spectra of molecules considered to be surface enhanced

High resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED) have been used to study the structure of adsorbed benzene (C₆H₆ and C₆D₆) monolayers on the Rh(111) surface at 300K. A surface bonding geometry is proposed for benzene adsorbed to give a c(2?3×4) rectangular structure, which involves very little perturbation of the molecular structure with the ring plane parallel to the surface. Only one chemical environment for adsorbed benzene is indicated by a single frequency shift of the symmetric CH out-of-plane bending mode. The adsorption site is tentatively assigned to benzene centered over a single Rh atom.     

Modelling the interaction in a benzene dimer

The interaction between aromatic rings is a fundamental problem in material science and biochemistry. These interactions are generally found to stabilise protein molecules and the double helical structure of DNA, and they also play an important role in the recognition processes in biological and non-biological systems. However, the complexity and variety in the structures and components of aromatic compounds are major obstacles to investigating their interactions. In this study, the simplest case of aromatic interactions, which is the interaction between two benzene rings, is modelled using a continuous approximation. Assuming a constant atomic surface density and modelling the structure of a benzene molecule as a combination of two rings, namely an inner carbon ring and an outer hydrogen ring, the van der Waals interaction between any two benzene rings can be obtained as the sum of four interactions. The major result obtained here is an analytical expression for the potential energy which can then be used to predict equilibrium configurations for two interacting benzene molecules. Moreover, we find that at sufficiently large distances between the two benzene molecules, the orientational angle φ at which the interaction energy is a minimum can be approximated by the arctan of the ratio of two separation distances in two mutually perpendicular directions.     

Photoelectron spectroscopic studies of the butylbenzenes

The He(I) photoelectron spectra of the geometrical isomers of butylbenzene have been compared. All the isomers have first ionization potentials within 0.08 eV but show variations in the higher ionization energy range. A valence-electron-only model potential (VEOMP-3G) method is employed to aid in the spectral assignment. Comparison with the spectra of benzene and the butyl moiety indicates that the spectra of the butylbenzenes can be interpreted according to a composite-molecule model, which indicates that CC as well as CH hyperconjugation must be invoked to adequately describe the benzene—butyl interactions.     

Local spectroscopy of image-potential-derived states: from single molecules to monolayers of benzene on Cu(111)

Stark-shifted image-potential states were measured with an STM tip for benzene adsorbed on a Cu(111) surface. A single benzene molecule locally shifts the position of the first image state toward the Fermi level by 0.2 eV relative to its position on the clean surface. The energetic position of this molecule-modified state shifts to lower energy with increasing coverage of benzene on the surface. This is attributed to local surface potential changes that are correlated with the lowering of the crystal work function due to adsorption of benzene.     

Shock-Induced Phase Transformations in Melt Pockets within Martian Meteorite NWA 4468

Northwest Africa (NWA) 4468 is a 675 g Martian meteorite recovered from the Western Sahara in 2006. It is an olivine basaltic shergottite, comprising clinopyroxene, olivine, maskelynite, chromite, ilmenite, Ca-phosphate polymorphs, troilite, and pyrrhotite. The sample shows both bulk (maskelynite formation) and localized shock effects (pressure-temperature excursions in veins and melt pockets). Here we report the presence of high-pressure polymorphs in melt pockets. We have discovered three phosphate polymorphs in the melt pockets (chlorapatite, merrillite, and tuite). Their crystal structure has been confirmed by Raman analysis. The mineral assemblages of the melt pockets are indicative of solid-state transformations, nucleation, and recrystallization at high temperatures and pressures. The stability fields of these minerals are used to infer the pressure and temperature conditions reached locally in the melt pockets as 23 GPa and 2000°C.     

Benzene adsorption and oxidation on Ir(1 1 1)

Adsorption, decomposition and oxidation of benzene on Ir(1 1 1) was studied by high resolution (synchrotron) XPS, temperature programmed desorption and low energy electron diffraction. Molecular adsorption of benzene on Ir(1 1 1) is observed between 170 K and 350 K. Above this temperature both desorption and decomposition of benzene take place. An ordered adsorbate structure was observed upon adsorption around 335 K. Decomposition involves C-C bond breaking as the formation of CH_ad is observed. The presence of a saturated O_ad layer (0.5 ML) weakens molecular benzene adsorption and suppresses decomposition.