Examination of charge alternation in CH4 and CH3F from ab initio LCAO SCF MO wavefunctions and their localized bond orbitals

The question of whether or not fluorine substitution produces charge alternation is examined for CH₄ and CH₃F. Two sets of ab initio LCAO SCF MO wavefunctions (one a 3 G STO based one, the other a double zeta based one) are analyzed via charge density, localized CH bond moment, and population analysis calculations. Although both sets of wavefunctions show a slightly more negative H region in CH₃F relative to CH₄, in qualitative agreement with earlier work by Pople et al., the differences are small, and their sources are not clear. For example, in the 3 G calculations the CH localized orbital is the essential source of the increased density in CH₃F, while for the double zeta calculations the increased density is due to the tail of an F lone-pair orbital trans to the CH bond. Consideration of details of these studies as well as those from large STO based SCF MO wavefunctions by Arrighini et al., suggests that one will need very accurate wavefunctions to resolve the problem unambiguously.The Radiation Laboratory is operated under contract with the U.S. Atomic Energy Commission. This is AEC document no. COO-38-847.     

L'utilisation d'orbitales localisées dans l'étude théorique des molécules

The five simplest alkanes have been studied in terms of localized orbitals. The transferability of the Fock matrix elements in this basis allows us to elaborate a simple parametric procedure adapted for saturated hydrocarbons. Some original applications of this procedure are performed.

     

An analytic study of the E ⊗ e Jahn-Teller polaron

An analytic study is presented of the E⊗e Jahn-Teller (JT) polaron, consisting of a mobile e_g electron linearly coupled to the local e_g normal vibrations of a periodic array of octahedral complexes. Due to the linear coupling, the parity operator and the angular momentum operator commute with the JT part and cause a twofold degeneracy of each JT eigenvalue. This degeneracy is lifted by the anisotropic hopping term. The Hamiltonian is then mapped onto a new Hilbert space, which is isomorphic to an eigenspace of belonging to a fixed angular momentum eigenvalue j > 0. In this representation, the Hamiltonian depends explicitly on j and decomposes into a Holstein term and a residual JT interaction. While the ground state of the JT polaron is shown to belong to the sector j = 1/2, the Holstein polaron is obtained for the “unphysical” value j = 0. The new Hamiltonian is then subjected to a variational treatment, yielding the dispersion relations and effective masses for both kinds of polarons. The calculated polaron masses are in remarkably good agreement with recent quantum Monte Carlo data. The possible relevance of our results to the magnetoresistive manganite perovskites is briefly discussed. Received 6 July 2001     

扫描微电极法原位测量2024Al合金表面微区Cl~-浓度分布

应用自研制扫描微电极测量系统和扫描微Ag/AgCl复合电极 ,原位测量含Cl- 溶液中 ,2 0 2 4Al合金在其局部腐蚀发生发展过程中金属 /溶液界面微区Cl- 离子的浓度分布 ,考察金属 /溶液界面微区Cl- 浓度分布对Al合金表面局部腐蚀行为的影响 .结果表明 ,扫描Ag/AgCl探针可实时跟踪腐蚀过程中金属表面氯离子浓度分布的动态行为 .当 2 0 2 4Al合金浸渍于含Cl- 溶液中 ,Cl- 离子在Al合金 /溶液界面呈不均匀分布 ,Cl- 主要在第 2相颗粒和铝基交界区域发生优先吸附和累积 ,从而促进局部腐蚀的发生和发展     

Localized Surface Plasmon Resonance of Cu@Cu2O core-shell nanoparticles: Absorption, Scattering and Luminescence

By co-deposition via RF-Sputtering and RF-PECVD methods and using Cu target and acetylene gas, we prepared Cu@Cu₂O core-shell nanoparticles on the a-C:H thin film at room temperature. Mie absorption of Cu cores, scattering from Cu₂O shell and luminescence that rises from carrier transfer in Cu@Cu₂O interface were employed to fit the whole range of visible extinction spectrum of these core-shells. From simulation it was found that scattering and luminescence have an important effect on the energy, width and shape of LSPR absorption peak. Shift of LSPR peak is more affected by the dielectric coefficient of shell than Cu core size particularly for Cu core diameter above 4 nm. Also, the LSPR absorption peak is damped by decreasing Cu core size and dielectric coefficient of shell. The energy of LSPR absorption peak is independent of shell thickness and host dielectric coefficient. The LSPR peak is damped by increasing shell thickness and host dielectric coefficient too. The scattering contribution in extinction spectra was affected more by shell size than dielectric coefficient. These points are important for detection techniques based on LSPR peak.     

On a common critical state in localized and diffuse failure modes

Accurately modeling the critical state mechanical behavior of granular material largely relies on a better understanding and characterizing the critical state fabric in different failure modes, i.e. localized and diffuse failure modes. In this paper, a mesoscopic scale is introduced, in which the organization of force-transmission paths (force-chains) and cells encompassed by contacts (meso-loops) can be taken into account. Numerical drained biaxial tests using a discrete element method are performed with different initial void ratios, in order to investigate the critical state fabric on the meso-scale in both localized and diffuse failure modes. According to the displacement and strain fields extracted from tests, the failure mode and failure area of each specimen are determined. Then convergent critical state void ratios are observed in failure area of specimens. Different mechanical features of two kinds of meso-structures (force-chains and meso-loops) are investigated, to clarify whether there exists a convergent meso-structure inside the failure area of granular material, as the signature of critical state. Numerical results support a positive answer. Failure area of both localized and diffuse failure modes therefore exhibits the same fabric in critical state. Hence, these two failure modes prove to be homological with respect to the concept of the critical state.     

Localized plastic strain in polycrystalline materials with hole and notches

Analyzed numerically are the localized strain of polycrystalline materials subjected to quasi-static loading. The objective is to study the peculiarities associated with the deformation process close to the stress concentrators such as holes, notches and interfaces of internal structure. Analytical results show that geometry and/or heterogeneous internal structure of material together with the action of maximum shear result in the development of a system of plastically deformed shear bands. Shears and rotations in the regions of strain localization are found to be higher than in other parts of the specimen while rotations are more sensitive to localization.     

Evolution de la fonction de répartition d'un gaz de tourbillons 2D en présence d'un bruitEvolution of the repartition function of 2D vortex gaz in presence of noise

In this work, we study the motion of N localized vortices in the presence of ‘noise’. To apply the methods of statistical mechanics, we determine the evolution equation for the probability density function of vortices in which the presence of the ‘noise’ is accounted for by as a term similar to viscosity. This equation is isomorph to the system of equations which describe 2D turbulence with viscosity. The advantage of this formulation is that it can be numerically implemented at very large Reynolds numbers. To cite this article: S. Decossin, V. Pavlov, C. R. Mecanique 331 (2003).     

Non-linear behavior of delaminated unidirectional sandwich panels with partial contact and a transversely flexible core

The paper presents the results of an investigation of the non-linear behavior of delaminated sandwich panels with a compressible core. The delaminated zone, at one of the face-core interfaces, consists of through-the-width crack, which is free of shear stresses but is capable of accommodating partial contact with compressive stresses only within the debonded zone. The governing non-linear equations along with the appropriate boundary conditions and the continuity conditions are derived through variational principles. The governing equations include moderate deformations type of kinematic relations, and include the high-order effects due to the transverse flexibility of the core. The governing equations along with the stress and displacements fields for the core and the appropriate continuity conditions are presented. The effects of the non-linear response and the partial contact are described through some numerical cases of three points bending typical sandwich panels with inner delaminations in the vicinity of a concentrated load, in the vicinity of a stiffened core and, finally, far from the load. Numerical results in the form of displacements, bending moments, shear stresses in the core and vertical interfacial normal stresses at the upper and lower face-core interfaces along the panel length and at the delamination crack tips are presented. Buckling curves of load versus various extreme structural parameters are included. The analyses show that a full contact type of delamination transforms into a partial contact area with buckling of the compressed face sheet, as the load is increased and it is associated with extreme large displacements and stresses.     

Breathers and localized solitons for the Hirota–Maxwell–Bloch system on constant backgrounds in erbium doped fibers

In nonlinear erbium doped fibers, the Hirota–Maxwell–Bloch system with higher order effects usually governs the propagation of ultrashort pulses. New soliton solutions for this system are constructed on the constant backgrounds including one and two breathers and first and higher order localized soliton solutions. Considering the influence of higher order effects, propagation properties of those soliton solutions are discussed.