A density-functional-theory-based finite element model to study the mechanical properties of zigzag phosphorene nanotubes

In this paper, the density functional theory calculations are used to obtain the elastic properties of zigzag phosphorene nanotubes. Besides, based on the similarity between phosphorene nanotubes and a space-frame structure, a three-dimensional finite element model is proposed in which the atomic bonds are simulated by beam elements. The results of density functional theory are employed to compute the properties of the beam elements. Finally, using the proposed finite element model, the elastic modulus of the zigzag phosphorene nanotubes is computed. It is shown that phosphorene nanotubes with larger radii have larger Young's modulus. Comparing the results of finite element model with those of density functional theory, it is concluded that the proposed model can predict the elastic modulus of phosphorene nanotubes with a good accuracy.     

A first principles lattice dynamics and Raman spectra of the ferroelastic rutile to CaCl2 phase transition in SnO2 at high pressure

A first principles calculation of the lattice dynamical properties of rutile SnO₂ has been performed using density functional perturbation theory at ambient and high‐pressure conditions to understand the pressure‐induced phase transition. The calculated zone centre phonon modes at ambient and high pressures have been compared with Raman scattering and infrared measurements. Full phonon dispersion curves and phonon densities of states and Raman intensities at high pressures are calculated and given for the first time in literature. The ferroelastic transition from the rutile to the CaCl₂‐type structure was confirmed. It is clearly illustrated that the first transition is associated with macroscopic shear instability which arises from the strong coupling between elastic constants and softening of Raman active B_1g mode. The observed pressure of phase transition in experimental measurements was reproduced more accurately than in previous calculations, and the difference between observed and calculated transition pressure is only of the order of 2%. The mode Grüneisen parameter is quantitatively as well as qualitatively different from the earlier reported values. Copyright © 2013 John Wiley & Sons, Ltd.     

DFT calculations of XPS/NEXAFS and IR spectra to elucidate the reaction products of acetonitrile with Si(0 0 1)-2 × 1

NEXAFS data [S. Rangan et al., Phys. Rev. B 71 (2005) 165319] and FTIR data [M.P. Schwartz, R.J. Hamers, Surf. Sci. 601 (2007) 945] apparently do not converge in the identification of the reaction products of acetonitrile (CH₃CN) with Si(0 0 1)-2 × 1 at room temperature. Using DFT calculations of core-excited/core-ionized spectra and of IR vibrational frequencies and intensities, we show the consistency of the body of experimental data. Three species are present on the surface in equivalent amounts, a CN moiety, a pendent CN and a CCN ketenimine submitted to a strong twist imposed by the Si bond directionality. More generally, the paper shows the usefulness of spectroscopic data simulations in the elucidation of complex surface chemistry problems.     

Intermediates in the hydrogenation of benzene to cyclohexene on Pt(1 1 1) and Pd(1 1 1): A comparison from DFT calculations

Catalytic hydrogenation of aromatic compounds is an important process in petroleum industry. Understanding it through experimental or theoretical research can help to improve its efficiency. This work presents a first principles density functional theory study of the intermediates for the first four hydrogenations steps of the smallest aromatic compound, benzene, into C₆H₁₀ species, on two popular catalytic metals, palladium and platinum, described by periodic models. Different structures have been studied for the intermediate C₆H_6+n species, with a various degree of conservation of the conjugation. Some intermediates would present in gas phase a closed-shell conjugated structure, while other would correspond to multiple radicals with a massive destruction of the benzene π system. The Pd and Pt(1 1 1) surfaces strongly differ in terms of most stable structure for the intermediates. On Pd the most conjugated intermediates, i.e. the most stable in gas phase, is clearly preferred. In contrast, on Pt, multiple radical species, highly unstable in gas phase, are strongly stabilized by coupling with the surface. This thermodynamic study indicates a different trend for the hydrogenation mechanism: a clear successive 1-2-3… hydrogenation of neighboring carbon atoms on Pd keeping the largest conjugated fragment, and a nonconsecutive attack, with a maximum breaking of benzene conjugation on Pt.     

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

The optical properties of several azobenzene derivatives were modulated by varying the dipole moments and conjugation lengths of the D‐π‐A systems. The relationship between the structure and absorption spectrum and polarizability was studied in the gas phase, THF and MeOH solutions, respectively, by using the density functional theory. The calculated absorption spectra and second‐order polarizabilities are in good agreement with the available experimental observations. In comparison with the D‐π‐A monomer, the H‐shaped D‐π‐A dimer almost doubles the dipole moments and hence increases the second‐order polarizabilities, without a significant shift in the maximum absorption bands. The addition of another azobenzol group between electron‐donating and ‐accepting groups increases the second‐order polarizabilities by 4–6 times, but leads to an evident red‐shift of about 65–80 nm in spectra. The relative second‐order polarizability of the halogen‐substituted derivatives is in the sequence of ? CF₃ > ? F > ? Cl > ? Br, without obvious substituent effects on the optical transparency. The D‐π‐A chromophores with the strong electron‐donating (amino) and ‐accepting (acetyl) substituent present the larger second‐order polarizabilities, at the cost of about 20 nm red‐shift of the maximum absorption lengths relative to the halogen‐substituted species. It is also demonstrated that both the linear and nonlinear optical properties augment with the increase in solvent polarity, accompanied by a red‐shift in the wavelengths of maximum absorption by about 18 and 23 nm, respectively, in THF and MeOH solutions. The changes in optical properties upon the structural modifications are further rationalized by the electronic structures of various H‐shaped dimers. Copyright © 2010 John Wiley & Sons, Ltd.     

A DNS study of the physical mechanisms associated with density ratio influence on turbulent burning velocity in premixed flames

Data obtained in 3D direct numerical simulations of statistically planar, 1D weakly turbulent flames characterised by different density ratios σ are analysed to study the influence of thermal expansion on flame surface area and burning rate. Results show that, on the one hand, the pressure gradient induced within a flame brush owing to heat release in flamelets significantly accelerates the unburned gas that deeply intrudes into the combustion products in the form of an unburned mixture finger, thus causing large-scale oscillations of the burning rate and flame brush thickness. Under the conditions of the present simulations, the contribution of this mechanism to the creation of the flame surface area is substantial and is increased by σ, thus implying an increase in the burning rate by σ. On the other hand, the total flame surface areas simulated at σ = 7.53 and 2.5 are approximately equal. The apparent inconsistency between these results implies the existence of another thermal expansion effect that reduces the influence of σ on the flame surface area and burning rate. Investigation of the issue shows that the flow acceleration by the combustion-induced pressure gradient not only creates the flame surface area by pushing the finger tip into the products, but also mitigates wrinkling of the flame surface (the side surface of the finger) by turbulent eddies. The latter effect is attributed to the high-speed (at σ = 7.53) axial flow of the unburned gas, which is induced by the axial pressure gradient within the flame brush (and the finger). This axial flow acceleration reduces the residence time of a turbulent eddy in an unburned zone of the flame brush (e.g. within the finger). Therefore, the capability of the eddy for wrinkling the flamelet surface (e.g. the side finger surface) is weakened owing to a shorter residence time.     

Use of micro‐Raman spectrometry coupled with scanning electron microscopy to determine the chemical form of uranium compounds in micrometer‐size particles

In the frame of nuclear safeguards, knowledge of the chemical form (stoichiometry) of the uranium compounds present in the micrometric particulate material sampled by wiping surfaces in an inspected nuclear facility may point out the industrial process implemented in the installation. Micro‐Raman spectroscopy (MRS) coupled with scanning electron microscopy (SEM) has been used for the first time to analyze micrometer‐size particles of various uranium oxides [UO₂, U₃O₈, UO₃, and UO₄ · 4(H₂O)] deposited on carbon disks. Uranium particles are detected by means of SEM, and Raman analysis is then directly carried out inside the SEM measurement chamber without moving the carbon disk from SEM to MRS. When particles are deposited on appropriate carbon disks (sticky carbon tapes), despite a loss of signal‐to‐noise ratio of about an order of magnitude with regard to the stand‐alone MRS, all uranium oxides are successfully identified in particles by in‐SEM Raman analysis, obtaining similar characteristic bands as the ones obtained with the stand‐alone MRS. Moreover, with the SEM–MRS coupling, particles as small as 1 µm can be analyzed, whereas, without the SEM–MRS coupling, only particles larger than ~5 µm are efficiently analyzed, after localization inside the SEM, transfer of the sample holder into the MRS, and relocation of the particles inside the MRS. Copyright © 2013 John Wiley & Sons, Ltd.     

Prediction of the phase transition from ferromagnetic perovskite to non-magnetic post-perovskite in SrRuO3 : A first-principles study

The phase transition in the perovskite (Pv) SrRuO₃ under pressure has been studied by using first-principles calculations based on density functional theory. The post-perovskite (Ppv) phase transition of SrRuO₃ will take place under hydrostatic pressure of about 40 GPa. The stability of Ppv- SrRuO₃ is justified by the enthalpy calculations, and this phase transition accompanies volume disconnection and magnetic moment collapses. The crystallographic data and the electronic structure of Ppv- SrRuO₃ are also predicted. The crystal structure of Ppv- SrRuO₃ is similar to that of Ppv- CaRuO₃. A non-magnetic ground state is found in Ppv- SrRuO₃. The strong hybridization of Ru and O is evident in the electronic structures of both phases. We expect that these results will help further understanding of SrRuO₃ under high pressure.     

A novel approach to determine leucomalachite green and malachite green in fish fillets with surface‐enhanced Raman spectroscopy (SERS) and multivariate analyses

The use of illegal fish drugs, such as malachite green (MG) in aquaculture has raised growing concerns over the safety of aquatic food products, and sensitive and rapid methods for detection of these drugs in fish muscle are much needed. Simplified extraction methods coupled with surface‐enhanced Raman spectroscopy were used for analysis of MG and its metabolite leucomalachite green (LMG) in tilapia fillets containing 0–50 ng g⁻¹ LMG or MG. Principal component analysis and partial least squares (PLS) regression were used for spectral data analyses. High sensitivity (MG or LMG could be detected at 1–2 ng g⁻¹ levels) and PLS models with good predictability [root mean square error of validation (RMSEV) = 1.97–2.21 ng g⁻¹, R² = 0.984–0.988] were possible with suitable sample extraction methods. The simplest extraction method developed provided an RMSEV of 9.32 ng g⁻¹ and R² of 0.788, and although this was not ideal, detection of MG and LMG at 5 ng g⁻¹ level with this method could reduce sample throughput time and provide for faster detection of LMG and MG. Copyright © 2012 John Wiley & Sons, Ltd.     

A composite high-pressure cell with sintered diamond insets for study of thermoelectric and thermomagnetic properties in a range up to 30 GPa: Application to Pr and PbTe

A composite high-pressure cell with the sintered diamond insets is reported to be an effective tool for investigation of transport properties of solids under pressure as high as ∼30 GPa. The temperature distribution inside the cell was calculated. Using this cell, the pressure-driven phase transitions in praseodymium (Pr) have been studied by the thermopower technique (Seebeck effect). The results have shown that a scenario of the phase transitions in Pr (existence of the monoclinic C2/m phase) crucially depends on defects and distortions in a crystal lattice. So, the monoclinic phase was noticeable only for the first pressurization cycle. A technique of measurement of the longitudinal and the transverse thermomagnetic Nernst-Ettingshausen (N-E) effects (magnetothermopower) under high P is explained. With an example of lead telluride (PbTe), it is demonstrated that magnetic field can significantly improve the thermoelectric efficiency under pressure. The merits of the cell developed are discussed concerning basic research and technologies.     

Genetic Algorithms as a tool in the study of aperiodic order,with application to the case of X-Ray diffraction spectra of GaAs-AlAs multilayer heterostructures

We present the first application of Genetic Algorithms to the analysis of data from an aperiodically ordered system, high resolution X-Ray diffraction spectra from multilayer heterostructures arranged according to a deterministic or random scheme. This method paves the way to the solution of the “inverse problem”, that is the retrieval of the generating disorder from the investigation of the spectra of an unknown sample having non crystallographic, non quasi-crystallographic order. Received 18 March 2002 / Received in final form 3 July 2002 Published online 31 October 2002 RID="a" ID="a"e-mail: Evelyne.Lutton@inria.fr RID="b" ID="b"CNRS UMR 8502     

Volumetric and viscometric study of molecular interactions in the mixtures of some secondary alcohols with equimolar mixture of ethanol and N,N-dimethylacetamide at 308.15 K

Densities and viscosities of mixtures of isopropanol, isobutanol and isoamylalcohol with equimolar mixture of ethanol and N,N-dimethylacetamide have been measured at 308.15 K over the entire composition range. Deviations in viscosity, excess molar volume and excess Gibb’s free energy of activation of viscous flow have been calculated from the experimental values of densities and viscosities. Excess properties have been fitted to the Redlich-Kister type polynomial equation and the corresponding standard deviations have been calculated. The experimental data of viscosity have been used to test the applicability of empirical relations of Grunberg-Nissan, Hind-McLaughlin, Katti-Chaudhary and Heric-Brewer for the systems studied. Molecular interactions in the liquid mixtures have been investigated in the light of variation of deviation and of excess values in evaluated properties.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

A flexible blue light sensitive organic photodiode with high properties for the applications in low‐voltage‐control circuit and flexion sensors

Low‐voltage‐control circuit is one of the most important parts of the modern electrical control system due to the avoidance of operation risk and easy automation. Here, based on a C₆₀: m‐MTDATA bulk heterojunction, a blue‐light‐sensitive organic photodiode (OPD) is explored for the development of flexible low‐voltage‐control circuit. The control of circuit under 2000 V high voltage is achieved. The influences of the organic‐layer thickness, the donor/acceptor volume ratio and the matching of energy levels on the photocurrent are investigated. The maximum light/dark current ratio and current transfer ratio of 1.3 × 10⁴ and 1.3% are achieved, respectively. The highest photoresponse is up to 130 mA/W, markedly higher than some commercial inorganic photodiodes. This device could also be used as flexion and mechanical force sensors with the current density changing under different bending conditions. Therefore, this sort of OPD has a promising application in low‐voltage‐controlled, high‐voltage‐endurable hands for intelligent robots.     

A Fabry-Perót type resonator tunable below 2 GHz for use in time domain rotational spectroscopy: Application to the measurement of the radio frequency spectra of bromobenzene and iodobenzene

Two aluminum mirrors with radii of 203.2 mm and radii of curvature also of 203.2 mm have been used to construct a tunable Fabry-Perót type resonator with Q values of ∼200 at frequencies as low as 500 MHz. The resonator has been incorporated into a pulsed nozzle, Fourier transform, Balle-Flygare spectrometer typically used for recording pure rotational spectra in the microwave region. The resonator design allows the instrument to access the radio frequency region (?3 GHz) of the electromagnetic spectrum. The spectrometer is of use in (i) recording low J transitions of large asymmetric molecules where the spectra are often greatly simplified compared to higher frequency regions; (ii) measuring hyperfine constants for heavy molecules with higher accuracy than may be obtained at higher frequencies where hyperfine structure may not be resolvable; and (iii) provides further synchronicity between laboratory based measurements and radio astronomy in the 30 cm region. The resonators use is illustrated by recording the rotational spectra of bromobenzene and iodobenzene. The lowest ΔJ = +1 transition for iodobenzene has been observed at 1130.5292(10) MHz.     

A DFT study on the formation of CH3O on Cu2O(1 1 1) surface by CH3OH decomposition in the absence or presence of oxygen

The formation mechanism of CH₃O by the adsorption and decomposition of CH₃OH on clean and oxygen-precovered Cu₂O(1 1 1) surface has been investigated with density functional theory method together with the periodic slab models. Two possible formation pathways of CH₃O by CH₃OH decomposition on oxygen-precovered (O_pre) Cu₂O(1 1 1) surface were proposed and discussed. One is the O-H bond-cleavage of CH₃OH with H migration to O_pre to form CH₃O; the other is the C-O bond-scission of CH₃OH with CH₃ migration to O_pre leading to CH₃O_pre. The calculated results show that the O-H bond-breaking path has the lowest activation barrier 26.8 kJ mol⁻¹, the presence of oxygen-precovered on Cu₂O(1 1 1) surface exhibits a high surface reactivity toward the formation of CH₃O by the O-H bond-cleavage of CH₃OH, and reduce the activation barrier of O-H bond-cleavage. The C-O bond-breaking path was inhibited by dynamics, suggesting that the O atom of CH₃O is not from the oxygen-precovered, but comes from the O of CH₃OH. Meanwhile, the calculated results give a clear illustration about the formation mechanism of CH₃O in the presence of oxygen and the role of oxygen at the microscopic level.     

Redox mechanism in the NiP<Subscript>2</Subscript> electrode for Li-ion batteries: A DFT study coupled with local chemical bond analyses

Li reactivity of the monoclinic NiP₂ electrode is investigated through first-principles density functional theory calculations and local chemical bond analysis. The stability of various Li _x NiP₂ is studied with respect to the conversion reaction . The T = 0K Li _x NiP₂ phase stability diagram, as obtained, reveals that several ternary phases of lithium composition Li₂NiP₂ can be electrochemically achieved upon reduction. They correspond to monoclinic or tetragonal structures in which Ni adopts a square-planar (D_4h-Li₂NiP₂) or a pseudo-tetrahedral (Td-Li₂NiP₂) environment. A local chemical bond analysis suggests that D_4h–Li₂NiP₂ would result from an interlayer P–P bond breaking induced by a two-phase (P redox) process, while Td-Li₂NiP₂ would result from a Jahn–Teller distortion associated with a single-phase (Ni–P redox) process. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. This paper was presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

A comprehensive study of the effect of <Emphasis Type="Italic">in situ</Emphasis> annealing at high growth temperature on the morphological and optical properties of self-assembled InAs/GaAs QDs

We investigate the effect of in situ annealing during growth pause on the morphological and optical properties of self-assembled InAs/GaAs quantum dots (QDs). The islands were grown at different growth rates and having different monolayer coverage. The results were explained on the basis of atomic force microscopy (AFM) and photo-luminescence (PL) measurements. The studies show the occurrence of ripening-like phenomenon, observed in strained semiconductor system. Agglomeration of the self-assembled QDs takes place during dot pause leading to an equilibrium size distribution. The PL properties of the QDs are affected by the Indium desorption from the surface of the QDs during dot pause annealing at high growth temperature (520°C) subsiding the effect of the narrowing of the dot size distribution with growth pause. The samples having high monolayer coverage (3.4 ML) and grown at a slower growth rate (0.032 ML s⁻¹) manifested two different QD families. Among the islands the smaller are coherent defect-free in nature, whereas the larger dots are plastically relaxed and hence optically inactive. Indium desorption from the island surface during the in situ annealing and inhomogeneous morphology as the dots agglomerate during the growth pause, also affects the PL emission from these dot assemblies.     

A comparative study of PFP and BAB models in predicting the excess thermo-acoustical and its allied properties of liquid ternary mixtures at 298.15 K

Densities and speed of sound were measured for six binaries and three ternary liquid systems. Excess acoustical and its allied properties like excess internal pressure, excess thermal pressure coefficient, excess pseudo-Gruneisen parameter, excess speed of sound and excess ultrasonic impendence, were evaluated with the help of perspective of two liquid models i.e. Prigogine–Flory–Patterson (PFP) and Bertrand–Acree–Bruchfield (BAB) at 298.15 K over a wide range of composition. The results so obtained from two liquid models are very much comparable and are in good agreement. A molecular interaction study has also been made successfully in the light of these excess acoustical properties.