Prediction of electronically nonadiabatic decomposition mechanisms of isolated gas phase nitrogen-rich energetic salt: Guanidium-triazolate

Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N-2, NH3, HNC, HCN, NH2CN and CH3NC), only NH3 (with NH2CN) and N-2 are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S-1 and S-0 surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt. (C) 2015 Elsevier B.V. All rights reserved.

Evidence for 3D isotropic long range spin-spin interaction near the ferromagnetic transition in bulk and thin film SrRuO3

In the case of metallic ferromagnets there has always been a controversy, i.e. whether the magnetic interaction is itinerant or localized. For example SrRuO3 is known to be an itinerant ferromagnet where the spin-spin interaction is expected to be mean field in nature. However, it is reported to behave like Ising, Heisenberg or mean field by different groups. Despite several theoretical and experimental studies and the importance of strongly correlated systems, the experimental conclusion regarding the type of spin-spin interaction in SrRuO3 is lacking. To resolve this issue, we have investigated the critical behaviour in the vicinity of the paramagnetic-ferromagnetic phase transition using various techniques on polycrystalline as well as (001) oriented SrRuO3 films. Our analysis reveals that the application of a scaling law in the field-cooled magnetization data extracts the value of the critical exponent only when it is measured at H -> 0. To substantiate the actual nature without any ambiguity, the critical behavior is studied across the phase transition using the modified Arrott plot, Kouvel-Fisher plot and M-H isotherms. The critical analysis yields self-consistent beta, gamma and delta values and the spin interaction follows the long-range mean field model. Further the directional dependence of the critical exponent is studied in thin films and it reveals the isotropic nature. It is elucidated that the different experimental protocols followed by different groups are the reason for the ambiguity in determining the critical exponents in SrRuO3.

Evidence for 3D isotropic long range spin-spin interaction near the ferromagnetic transition in bulk and thin film SrRuO3

In the case of metallic ferromagnets there has always been a controversy, i.e. whether the magnetic interaction is itinerant or localized. For example SrRuO3 is known to be an itinerant ferromagnet where the spin-spin interaction is expected to be mean field in nature. However, it is reported to behave like Ising, Heisenberg or mean field by different groups. Despite several theoretical and experimental studies and the importance of strongly correlated systems, the experimental conclusion regarding the type of spin-spin interaction in SrRuO3 is lacking. To resolve this issue, we have investigated the critical behaviour in the vicinity of the paramagnetic-ferromagnetic phase transition using various techniques on polycrystalline as well as (001) oriented SrRuO3 films. Our analysis reveals that the application of a scaling law in the field-cooled magnetization data extracts the value of the critical exponent only when it is measured at H -> 0. To substantiate the actual nature without any ambiguity, the critical behavior is studied across the phase transition using the modified Arrott plot, Kouvel-Fisher plot and M-H isotherms. The critical analysis yields self-consistent beta, gamma and delta values and the spin interaction follows the long-range mean field model. Further the directional dependence of the critical exponent is studied in thin films and it reveals the isotropic nature. It is elucidated that the different experimental protocols followed by different groups are the reason for the ambiguity in determining the critical exponents in SrRuO3.

A meso elastoplastic constitutive model for polycrystalline metals based on equivalent slip systems with latent hardening

A meso material model for polycrystalline metals is proposed, in which the tiny slip systems distributing randomly between crystal slices in micro-grains or on grain boundaries are replaced by macro equivalent slip systems determined by the work-conjugate principle. The elastoplastic constitutive equation of this model is formulated for the active hardening, latent hardening and Bauschinger effect to predict macro elastoplastic stress-strain responses of polycrystalline metals under complex loading conditions. The influence of the material property parameters on size and shape of the subsequent yield surfaces is numerically investigated to demonstrate the fundamental features of the proposed material model. The derived constitutive equation is proved accurate and efficient in numerical analysis. Compared with the self-consistent theories with crystal grains as their basic components, the present theory is much simpler in mathematical treatment.

Stiffness behaviour of injection moulded short glass fibre/impact modifier/polypropylene hybrid composites

The stiffness behaviour of injection moulded short glass fibre/impact modifier/polypropylene hybrid composites has been investigated in this work by theoretical predictions and experiments. Predictions from the self-consistent method were found to be in good agreement with test results for the impact modifier/polypropylene blends. By taking into account of the fibre orientation distributions in the skin and core layers, the values of Young's modulus for the skin and core layers were predicted by employing Eshelby's equivalent inclusion method and the average induced strain approach. The prediction of the values of Young's modulus for the whole sample was obtained by applying the simple mixture theory of laminated composites to the predicted results for the skin and core layers. Good correlation between predicted and experimental Young's modulus values were found.

An exact solution for the three-phase piezoelectric cylinder model under antiplane shear and its applications to piezoelectric composites

A three-phase piezoelectric cylinder model is proposed and an exact solution is obtained for the model under a farfield antiplane mechanical load and a far-field inplane electrical load. The three-phase model can serve as a fiber/interphase layer/matrix model, in terms of which a lot of interesting mechanical and electrical coupling phenomena induced by the interphase layer are revealed. It is found that much more serious stress and electrical field concentrations occur in the model with the interphase layer than those without any interphase layer. The three-phase model can also serve as a fiber/matrix/composite model, in terms of which a generalized self-consistent approach is developed for predicting the effective electroelastic moduli of piezoelectric composites. Numerical examples are given and discussed in detail.

A Study of Size-Dependent Microindentation

We recently proposed a strain gradient theory to account for the size dependence of plastic deformation at micron and submicron length scales. The strain gradient theory includes the effects of both rotation gradient and stretch gradient such that the rotation gradient influences the material character through the interaction between the Cauchy stresses and the couple stresses; the stretch gradient measures explicitly enter the constitutive relations through the instantaneous tangent modulus. Indentation tests at scales on the order of one micron have shown that measured hardness increases significantly with decreasing indent size. In the present paper, the strain gradient theory is used to model materials undergoing small-scale indentations. A strong effect of including strain gradients in the constitutive description is found with hardness increasing by a factor of two or more over the relevant range behavior. Comparisons with the experimental data for polycrystalline copper and single crystal copper indeed show an approximately linear dependence of the square of the hardness, H 2, on the inverse of the indentation depth, 1/h, I.e., H-2 proportional to 1/h, which provides an important self-consistent check of the strain gradient theory proposed by the authors earlier.

Effect of inclusions and holes on the stiffness and strength of honeycombs

A finite element study has been performed on the effects of holes and rigid inclusions on the elastic modulus and yield strength of regular honeycombs under biaxial loading. The focus is on honeycombs that have already been weakened by a small degree of geometrical imperfection, such as a random distribution of fractured cell walls, as these imperfect honeycombs resemble commercially available metallic foams. Hashin-Shtrikman lower and upper bounds and self-consistent estimates of elastic moduli are derived to provide reference solutions to the finite element calculations. It is found that the strength of an imperfect honeycomb is relatively insensitive to the presence of holes and inclusions, consistent with recent experimental observations on commercial aluminum alloy foams.

An incremental micromechanical scheme for nonlinear particulate composites

A general incremental micromechanical scheme for the nonlinear behavior of particulate composites is presented in this paper. The advantage of this scheme is that it can reflect partly the effects of the third invariant of the stress on the overall mechanical behavior of nonlinear composites. The difficulty involved is the determination of the effective compliance tensors of the anisotropic multiphase composites. This is completed by making use of the generalized self-consistent Mori-Tanaka method which was recently developed by Dai et al. (Polymer Composites 19(1998) 506-513; Acta Mechanica Solida 18 (1998) 199-208). Comparison with existing theoretical and numerical results demonstrates that the present incremental scheme is quite satisfactory. Based on this incremental scheme, the overall mechanical behavior of a hard-particle reinforced metal matrix composite with progressive particle debonding damage is investigated.

Nucleated polymerization with secondary pathways. I. Time evolution of the principal moments.

Self-assembly processes resulting in linear structures are often observed in molecular biology, and include the formation of functional filaments such as actin and tubulin, as well as generally dysfunctional ones such as amyloid aggregates. Although the basic kinetic equations describing these phenomena are well-established, it has proved to be challenging, due to their non-linear nature, to derive solutions to these equations except for special cases. The availability of general analytical solutions provides a route for determining the rates of molecular level processes from the analysis of macroscopic experimental measurements of the growth kinetics, in addition to the phenomenological parameters, such as lag times and maximal growth rates that are already obtainable from standard fitting procedures. We describe here an analytical approach based on fixed-point analysis, which provides self-consistent solutions for the growth of filamentous structures that can, in addition to elongation, undergo internal fracturing and monomer-dependent nucleation as mechanisms for generating new free ends acting as growth sites. Our results generalise the analytical expression for sigmoidal growth kinetics from the Oosawa theory for nucleated polymerisation to the case of fragmenting filaments. We determine the corresponding growth laws in closed form and derive from first principles a number of relationships which have been empirically established for the kinetics of the self-assembly of amyloid fibrils.

Micromechanics Modeling Of Strength For Nanocrystalline Copper

We present a model in this paper for predicting the inverse Hall-Petch phenomenon in nanocrystalline (NC) materials which are assumed to consist of two phases: grain phase of spherical or spheroidal shapes and grain boundary phase. The deformation of the grain phase has an elasto-viscoplastic behavior, which includes dislocation glide mechanism, Coble creep and Nabarro-Herring creep. However the deformation of grain boundary phase is assumed to be the mechanism of grain boundary diffusion. A Hill self-consistent method is used to describe the behavior of nanocrystalline pure copper subjected to uniaxial tension. Finally, the effects of grain size and its distribution, grain shape and strain rate on the yield strength and stress-strain curve of the pure copper are investigated. The obtained results are compared with relevant experimental data in the literature.

Two-dimensional fluid model simulation of bell jar top inductively coupled plasma

In the present paper, argon (Ar) plasmas in a bell jar inductively coupled plasma (ICP) source are systematically studied over pressures from 5 to 20 mtorr and power inputs from 0.2 to 0.5 kW. In this study, both a two-dimensional (2-D) fluid model simulation and global model calculation are compared, The 2-D fluid model simulation with a self-consistent power deposition is developed to describe the Ar plasma behavior as well as predict the plasma parameter distributions, Finally, a quantitative comparison between the global model and the fluid model is made to test their validity.

Mechanical modeling of grain boundary sliding of polycrystals

Using a variational method, a general three-dimensional solution to the problem of a sliding spherical inclusion embedded in an infinite anisotropic medium is presented in this paper. The inclusion itself is also a general anisotropic elastic medium. The interface is treated as a thin interface layer with interphase anisotropic properties. The displacements in the matrix and the inclusion are expressed as polynomial series of the cartesian coordinate components. Using the virtual work principle, a set of linear algebraic equations about unknown coefficients are obtained. Then the general sliding spherical inclusion problem is accurately solved. Based on this solution, a self-consistent method for sliding polycrystals is proposed. Combining this with a two-dimensional model of an aggregate polycrystal, a systematic analysis of the mechanical behaviour of sliding polycrystals is given in detail. Numerical results are given to show the significant effect of grain boundary sliding on the overall mechanical properties of aggregate polycrystals.

Micromechanics of elastic solids weakened by a large number of cracks

This paper presents a micromechanics analysis of the elastic solids weakened by a large number of microcracks in a plane problem. A new cell model is proposed. Each cell is an ellipse subregion and contains a microcrack. The effective moduli and the stress intensity factors for an ellipse cell are obtained. The analytic closed formulas of concentration factor tensor for an isotropic matrix containing an anisotropic inclusion are derived. Based on a self-consistent method, the effective elastic moduli of the solids weakened by randomly oriented microcracks are obtained.

Evolution and propagation of density waves on galactic disk .1. General evolution equation of wavelet and discussion of its solution

This paper presents a general self-consistent theory of evolution and propagation of wavelets on the galactic disk. A simplified model for this theory, i. e. the thin transition-layer approximation is proposed.There are three types of solutions to the basic equation governing the evolution of wavelets on the disk: (ⅰ) normal propagating type; (ⅱ) swing type; (ⅲ) general evolving type. The results show that the first two types are applicable to a certain domain on the galactic disk and a certain region of the wave number of wavelets. The third is needed to join the other two types and to yield a coherent total picture of the wave motion. From the present theory, it can be seen that the well-known "swing theory" of the G-L sheet model holds only for a certain class of basic states of galaxies.