A theoretical study on the nonlinear optical second-order properties of azobenzene series molecules

On the basis of AM1 and INDO/CI methods, we devise the program for the calculation of nonlinear second-order optical susceptibilities beta(ijk) and perform systematic theoretical studies on the nonlinear optical second-order properties of azobenzene series molecules, i. e. on the basis of [GRAPHICS] we induced different donors on the left side of phenyl ring, and different accepters on the right side of phenyl ring, and examined the rule of beta variation. The regularity summarized from the calculated results has been explained micromechanically. Finally, a molecule having a big nonlinear second-order optical susceptibility has been designed.

Probabilistic distribution of one-phase structure seminvariants for an isomorphous pair of structures: Theoretical basis and initial applications

Given a special type of triplet of reciprocal-lattice vectors in the monoclinic and orthorhombic systems, there exist eight three-phase structure seminvariants (3PSSs) for a pair of isomorphous structures. The first neighborhood of each of these 3PSSs is defined by the six magnitudes and the joint probability distribution of the corresponding six structure factors is derived according to Hauptman's neighborhood principle. This distribution leads to the conditional probability distribution of each of the 3PSSs, assuming as known the six magnitudes in its first neighborhood. The conditional probability distributions can be directly used to yield the reliable estimates (0 or pi) of the one-phase structure seminvariants (1PSSs) in the favorable case that the variances of the distributions happen to be small [Hauptman (1975). Acta Cryst. A31, 680-687]. The relevant parameters in the formulas for the monoclinic and orthorhombic systems are given in a tabular form. The applications suggest that the method is efficient for estimating the 1PSSs with values of 0 or pi.

FORMATION OF [C60C5H5] ADDUCT CATIONS AND THEORETICAL-STUDY OF THE ISOMERS

We study here the reactions between C-60 and planar C5H5+ cations that lead to the formation of [C60C5H5](+) adduct cations in the chemical ionization source of the mass spectrometer. The structures, stabilities and charge locations of some possible isomers of [C60C5H5](+): sigma-adduct, pi-complex, [1,4]- and [1,2]-addition cations, are studied by AM1 semiempirical molecular orbital calculations. We find that the most stable is the sigma-addition cation. Another interesting and stable structure is the pi-complex cation which is bonded by the electrostatic interaction at the inter-ring distance of 1.589 Angstrom with the C-5v symmetry. The C5H5+ cyclopentadienium cation seems to be an ''inverted umbrella'' sitting on a five-membered ring of the C-60 cage.

THEORETICAL-STUDIES ON THE CYCLIZATION PROCESS OF A NEW ORGANOSULFUR REACTION

The cyclization process of a new organosulfur reaction was studied by the MNDO (UHF) method. The first reaction path was assumed to be via the organosulfur radical intermediate, the second via the ionic (cationic and anionic) intermediates. The dehydroxylation process was assumed to occur with the synergistic cyclization. The results obtained indicate that the potential energy barrier of the first reaction path was about 102 kcal mol(-1), and although the formation of the ionic intermediate is comparatively difficult, the potential energy barrier of the second path is comparable to the first. The sequential reaction path via the radical intermediate, i.e. first cyclization, then dehydroxylation, was investigated for comparison. The cyclization reaction was found to be the thermodynamically favored process, while the ensuing dehydroxylation process was found to have a potential energy barrier of about 62 kcal mol(-1).

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

A theoretical framework of tracer methods for marine sediment dynamics

A new theoretical framework of tracer methods is proposed in the present contribution, on the basis of mass conservation. This model is applicable for both artificial and natural tracers. It can be used to calculate the spatial distribution patterns of sediment transport rate, thus providing independent information and verification for the results derived from empirical formulae. For the procedures of the calculation, first, the tracer concentration and topographic maps of two times are obtained. Then, the spatial and temporal changes in the concentration and seabed elevation are calculated, and the boundary conditions required are determined by field observations (such as flow and bedform migration measurements). Finally, based upon eqs. (1) and (13), the transport rate is calculated and expressed as a function of the position over the study area. Further, appropriate modifications to the model may allow the tracer to have different densities and grain size distributions from the bulk sediment.

Observation and theoretical analysis for the sand-waves migration in the North Gulf of South China Sea

According to the environmental characteristic of the north gulf of South China Sea, a quasi-3D mechanics model has been built for simulating the small scale sand-waves migration in the seas of southwest of Hainan Island. Based on the submarine micro-geomorphic data induced by multi-beam system and hydrographic survey record, the migrations of the sand-waves in the study area are predicted. The results show that calculation is consistent with the observation data in the groove of sand ridge, but not well in the crest of sand ridge. It is indicated that the mechanics model should be used to predict the migration of the small scale sand-waves which are dominated by bed load in the seas. This paper is very meaningful to project the route of submarine pipeline.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Theoretical investigation on the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111) surface

In this paper, the adsorption of Ag+ and hydrated Ag+ cations on clean Si(111) surface were investigated by using cluster (Gaussian 03) and periodic (DMol(3)) ab initio calculations. Si(111) surface was described with cluster models (Si14H17 and Si22H21) and a four-silicon layer slab with periodic boundary conditions. The effect of basis set superposition error (BSSE) was taken into account by applying the counterpoise correction. The calculated results indicated that the binding energies between hydrated Ag+ cations and clean Si(111) surface are large, suggesting a strong interaction between hydrated Ag+ cations and the semiconductor surface. With the increase of number, water molecules form hydrogen bond network with one another and only one water molecule binds directly to the Ag+ cation. The Ag+ cation in aqueous solution will safely attach to the clean Si(111) surface.

Theoretical study on adsorption of Na+ and Na+(H2O)(n) (n=1-6) on a clean Si(111) surface

To model the adsorption of Na+ in aqueous solution on the semiconductor surface, the interactions of Na+ and Na+(H2O)(n) (n = 1-6) with a clean Si(111) surface were investigated by using hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The Si(111) surface was described with Si8H12, Si16H20, and Si22H21 Cluster models. The effect of the basis set superposition error (BSSE) was taken into account by applying the counterpoise (CP) correction. The calculated results indicated that the interactions between the Na+ cation and the dangling bonds of the Si(111) surface are primarily electrostatic with partial orbital interactions. The magnitude of the binding energies depends weakly on the adsorption sites and the size of the clusters. When water molecules are present, the interaction between the Nal and Si(I 11) surfaces weakens and the binding energy has the tendency to saturate. On a Si22H21 cluster described surface, the optimized Na+-surface distance for Na+(H2O)(5) adsorbed at on-top site is 4.16 angstrom and the CP-corrected binding energy (MP2) is -35.4 kJ/mol, implying a weakly adsorption of hydrated Na+ cation on clean Si(111) surface.

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(111) surface

To evaluate the interactions between the atoms of An, Ag and Cu and clean Si(111) surface, two types of silicon clusters Si4H7 and Si16H20 together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from similar to 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom. (c) 2006 Elsevier B.V. All rights reserved.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

Theoretical and experimental research on time-optimal trajectory planning and control of industrial robots

提出了一种用于工业机器人时间最优轨迹规划及轨迹控制的新方法，它可以确保在关节位移、速度、加速度以及二阶加速度边界值的约束下，机器人手部沿笛卡尔空间中规定路径运动的时间阳短。在这种方法中，所规划的关节轨迹都采用二次多项式加余弦函数的形式，不仅可以保证各关节运动的位移、速度 、加速度连续而且还可以保证各关节运动的二阶加速度连续。采用这种方法，既可以提高机器人的工作效率又可以延长机器人的工作寿命以PUMA560机器人为对象进行了计算机仿真和机器人实验，结果表明这种方法是正确的有效的。它为工业机器人在非线性运动学约束条件下的时间最优轨迹规划及控制问题提供了一种较好的解决方案。

粘弹性介质中的地震波传播与波形反演研究

The real earth is far away from an ideal elastic ball. The movement of structures or fluid and scattering of thin-layer would inevitably affect seismic wave propagation, which is demonstrated mainly as energy nongeometrical attenuation. Today, most of theoretical researches and applications take the assumption that all media studied are fully elastic. Ignoring the viscoelastic property would, in some circumstances, lead to amplitude and phase distortion, which will indirectly affect extraction of traveltime and waveform we use in imaging and inversion. In order to investigate the response of seismic wave propagation and improve the imaging and inversion quality in complex media, we need not only consider into attenuation of the real media but also implement it by means of efficient numerical methods and imaging techniques. As for numerical modeling, most widely used methods, such as finite difference, finite element and pseudospectral algorithms, have difficulty in dealing with problem of simultaneously improving accuracy and efficiency in computation. To partially overcome this difficulty, this paper devises a matrix differentiator method and an optimal convolutional differentiator method based on staggered-grid Fourier pseudospectral differentiation, and a staggered-grid optimal Shannon singular kernel convolutional differentiator by function distribution theory, which then are used to study seismic wave propagation in viscoelastic media. Results through comparisons and accuracy analysis demonstrate that optimal convolutional differentiator methods can solve well the incompatibility between accuracy and efficiency, and are almost twice more accurate than the same-length finite difference. They can efficiently reduce dispersion and provide high-precision waveform data. On the basis of frequency-domain wavefield modeling, we discuss how to directly solve linear equations and point out that when compared to the time-domain methods, frequency-domain methods would be more convenient to handle the multi-source problem and be much easier to incorporate medium attenuation. We also prove the equivalence of the time- and frequency-domain methods by using numerical tests when assumptions with non-relaxation modulus and quality factor are made, and analyze the reason that causes waveform difference. In frequency-domain waveform inversion, experiments have been conducted with transmission, crosshole and reflection data. By using the relation between media scales and characteristic frequencies, we analyze the capacity of the frequency-domain sequential inversion method in anti-noising and dealing with non-uniqueness of nonlinear optimization. In crosshole experiments, we find the main sources of inversion error and figure out how incorrect quality factor would affect inverted results. When dealing with surface reflection data, several frequencies have been chosen with optimal frequency selection strategy, with which we use to carry out sequential and simultaneous inversions to verify how important low frequency data are to the inverted results and the functionality of simultaneous inversion in anti-noising. Finally, I come with some conclusions about the whole work I have done in this dissertation and discuss detailly the existing and would-be problems in it. I also point out the possible directions and theories we should go and deepen, which, to some extent, would provide a helpful reference to researchers who are interested in seismic wave propagation and imaging in complex media.

地震波散射非线性反演问题不动点理论及方法的研究

How to create a new method to solve the problem or reduce the influence of that the result of the seismic waves scattering nonlinear inversion is not uniqueness is a main purpose of this research work in the paper. On the background of research into the seismic inversion, new progress of the nonlinear inversion is introduced at the first chapter in this paper. Especially, the development, basic theories and assumptions on some major theories of seismic inversion are analyzed, discussed and summarized in mathematics and physics. Also, the problems faced by the mathematical basis of investigations of the seismic inversion are discussed, and inverse questions of strongly seismic scattering due to strong heterogeneous media in the Earth interior are analyzed and viewed. What the kernel of paper is that gathers all our attention making a new nonlinear inversion method of seismic scattering. The paper provides a theory and method of how to introduce the fixed-point theory into the nonlinear seismic scattering inversion and how to obtain the solution, and gives the actually method to create a serials of contractive mappings of velocity parameter's in the mapping space of wave. Therefore, the results testify the existence of fixed point of velocity parameter and give the method the find it. Further, the paper proves the conclusion that the value obtained by taking the fixed point of velocity parameter into wave equation is the fixed point of the wave of the contractive mapping. Thence, the fixed point is the global minima since the stabilities quality of the fixed point. Based on the new theory, in the chapter three, many inverse results are obtained in the numerical value test. By analysis the results one could find a basic facts that all the results, which are inversed by the different initial model, are tended to the true value in theoretical true model. In other words, the new method mostly eliminates the non-uniqueness that which is existed in seismic waves scattering nonlinear inversion in degree. But, since the test results are quite finite now, more test is need here to positive our theory. As a new theoretical method, it must be existed many weaken in it. The chapter four points out all the questions which is bother us. We hope more people to join us to solve the problem together.