Electro-optical properties of tetragonal KNbO<Subscript>3</Subscript>

Linear electro-optical tensor coefficients and optical susceptibility of tetragonal KNbO₃ are calculated using a formalism based on bond charge theory. Results are in close agreement with the experimental data. The covalent Nb-O bonding network comprising the distorted NbO₆ octahedral groups in the structure is found to be a major contributor to the electro-optic coefficients making these groups more sensitive to these properties than the KO₁₂ groups. The orientations of the chemical bonds play an important role in determining these properties.      

Nonlinear optical properties of (B3O7)5- and (B3O6)3- groups

3 O₅ (LBO) crystal has been studied by using the bond valence theory of complex crystals. Chemical bond parameters and linear and nonlinear optical (NLO) properties of each type of constituent chemical bonds are quantitatively determined. Because of the different crystal structure characteristics of LBO from those of β-BaB₂O₄ (BBO), the two anionic groups, (B₃O₇)^5- in LBO and (B₃O₆)^3- in BBO, play different roles in contributions to their own total NLO tensor coefficients of LBO and BBO, respectively. By comparison, we find that planar (B₃O₆)^3- groups are the ideal structure model, leading to little cancellation of contributions of each kind of bond in these groups, and this gives us a useful guide to design new NLO materials in the future. Received: 24 January 1997/Accepted: 27 March 1997     

Die Abweichungen von den Cauchy-Relationen

Qualitative rules for the deviations from the Cauchy relations are derived from experimental data. These departures are the components of a second rank tensor. The coefficients of “lateral interaction”c _iijj dominate in most cases over the correspondent shear resistancesc _ijij. Extreme effects of this type are generated by asymmetric lattice particles. Covalent bonds and other strong bonds with preferential orientation as well as strong overlap cause opposite effects. The departures from the Cauchy relations and the atomistic binding properties are very closely correlated.     

几种咪唑-二氧杂环的含能取代衍生物的理论研究

使用DFT的B3LYP方法对几种咪唑二氧杂环化合物的分子结构、红外光谱、生成焓、爆轰性能和化学/热稳定性进行了研究.四种不同含能基团-NO₂,-NH₂,-N₃和-ONO₂对该化合物各项性能的影响进行了比较.结果表明-NO₂和-ONO₂基团有效地增加了化合物的密度,而-N³基团极大地增加了化合物的生成焓.其中-NO₂取代物爆轰性能接近1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane,-ONO₂取代物的爆轰性能低于hexahydro-1,3,5-trinitro-1,3,5-triazine.自然键轨道分析表明,这些化合物中相对较弱的键为取代基和咪唑环之间的键,以及二氧杂环中的C-O键.吸电子基团(-NO₂, -N³和-ONO₂)在分子中产生了明显的诱导效应,减弱了基团与咪唑环之间的链接,降低了对应键的键裂解能.研究表明基团的电负性与化合物的稳定性有关.考虑到化合物的爆轰性能和热稳定性,DNTNDI化合物满足高能量密度材料的要求.     

晶体电光和非线性光学效应的离子基团理论(Ⅲ)——利用畸变氧八面体的离子基团模型计算LiNbO3,LiTaO3,KNbO3,BNN晶体的电光和倍频系数

本文用文献[1]中所提出的(MO₆)离子基团模型,计算LiNbO₃,LiTaO₃,KNbO₃,BNN等晶体的电光和倍频系数。假设在O_h对称时,这些晶体中的氧八面体具有相同的能级和对称波函数,则通过群表示理论就可得到在C_3ν,C_2ν对称性时氧八面体的能级和对称波函数,并进而用ABDP理论计算它们的电光和倍频系数。计算结果和实验符合得相当好。本文并从理论上解释了这些晶体的倍频系数大小、符号和氧八面体畸变间的关系,由此可以得到以下两个结论:(1)畸变氧八面体的离子基团模型不但适用于钙钛矿型材料,同时也适用于钨青铜型、LiNbO₃型材料。(2)在钨青铜型、LiNbO₃型的材料中,仍是“离子键”对电光和倍频效应作出主要贡献,同时由于LiTaO₃的共价键成份比LiNbO₃大,因而LiTaO₃的非线性光学效应比LiNbO₃小。     

晶体电光和非线性光学效应的离子基团理论(Ⅰ)——利用氧八面体畸变模型计算BaTiO3晶体电光及倍频系数

本文对钙钛矿型晶体的电光及倍频效应的机理提出了一个(MO₆)离子基团模型。并从(TiO₆)离子基团的准分子轨道及晶格场位能作用下的(TiO₆)离子基团的离子键轨道出发,利用ABDP理论,分别计算了BaTiO₃的各个电光及倍频系数。计算结果表明,在没有引入任何可调整参量的情况下,用(TiO₆)离子基团的晶格场理论所得到的电光及倍频系数的计算值和实验值符合得相当好,而准分子轨道对这些效应的贡献很小。由     

Infrared and Quantum-Chemical Studies of Dimethylsilane

Infrared spectra of (CH₃)₂SiH₂ and (CH₃)₂SiD₂ have been reinvestigated. Quantum-chemical calculations of geometry and force fields have been made at the HF, MP2, and B3LYP levels, followed by scaling of the force field with 14 independent parameters. Several vibration frequencies are reassigned. Bond lengths, force constants, scale factors, and electrical properties are compared with those in other methylsilanes. Both Si-H and Si-C bonds are weakened by α-methyl substitution. The C-H bonds in the methyl groups differ slightly in length and stretching frequency in ways familiar in hydrocarbons. An increase in SiH stretching intensity per bond with methylation is predicted theoretically and found by experiment. The sizes of the negative charges associated with both stretching and bending of the SiH bonds in the methylsilanes increase with the Mulliken charge with progressive methylation.     

Calculation of the components of the photoelastic effect in alkali-halide crystals

Calculations are made to determine the contribution of Lorentz-field and Coulomb-field anisotropy in alkali-halide crystals to the photoelastic coefficients p₁₁–p₁₂ and p₄₄ as well as to the piezopolarizability constants K, K, K_x, K_z, and K₀. These calculations are based on Mueller's theory of the photoelastic effect, with data on iron polarizability and photoelastic coefficients. The applicability of Mueller' s theory to the complete series of alkali-halide crystals is analyzed. Criteria are established for the ionicity of bonds in these crystals.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 28–34, December, 1975.     

Quantum-Chemical Investigation of the Intermolecular Interaction Effect on the Spectral-Luminescent and Physical-Chemical Properties of Certain 8-Azasteroid Class Molecules

The effect of hydrogen bonds on the spectral-luminescent and proton-acceptor properties of 8-azagone-12,17-dione and its 2,3-dimethoxy substituent is examined. The method of molecular electrostatic potential is used for choosing a spatial model for complexes with the 1:2 mixture ratio. Hydrogen bonding of oxygen atoms of C and D cycles of both molecules with water molecules is shown to affect but slightly the spectral-luminescent properties. The effect of hydrogen bonds on the proton-acceptor properties of molecules both in the ground and fluorescent states is most pronounced: the proton-acceptor properties of oxygen atoms of the C, D, and methoxy groups decrease, particularly in the fluorescent state, while the same properties of the nitrogen atom increase. We can assume on the basis of these facts that the role of the nitrogen atom in the intermolecular interaction is increased when it is in the S ₁ state.     

Ion-plasma treatment of Cd1 ? x Zn x Te (x ～ 0.04) single crystals and application of antireflection diamond-like carbon films

The influence of ion-plasma treatment of Cd_{1 ? x} Zn _x Te (x ?? 0.04) single crystals, which precedes the deposition of an antireflection coating (a diamond-like a-C: H: N film) on the optical properties of the resulting structure, is investigated. Treatment is carried out in an argon, nitrogen, and hydrogen plasma. As follows from the optical properties of the a-C: H: N/Cd_{1 ? x} Zn _x Te, the structure treated in an argon plasma offers the highest transmission. A model of the optical system is proposed that takes into account the formation of transition layers after ion-plasma treatment and the effect of the type of ion on their characteristics. The absorption spectra of the a-C: H: N/Cd_{1 ? x} Zn _x Te system are analyzed, and bands assigned to the stretching and bending vibrations of C-H bonds, as well as to C-C and C=O bonds, are revealed. The presence of these bonds should be taken into account in designing and synthesizing these optical coatings.     

Electronic, magnetic and transport properties of Co2TiZ (Z=Si, Ge and Sn): A first-principle study

We have studied the electronic structure, magnetic and transport properties of some Co based full Heusler alloys, namely Co₂TiZ (Z=Si, Ge and Sn), in the frame work of first-principle calculations. The calculations show that Co₂TiZ (X=Si, Ge and Sn) are to be half-metallic compounds with a magnetic moment of 2 μ_B, well consistent with the Slater-Pauling rule. The electronic structure results reveal that Co₂TiZ has the high density of states at the Fermi energy in the majority-spin state and show 100% spin polarization. Our results also suggest that both the electronic and magnetic properties in these compounds are intrinsically related to the appearance of the minority-spin gap. The origin of energy gap in the minority-spin states is discussed in terms of the electron splitting of Z (Z=Si, Ge and Sn) and 3d Co atoms and also the d-d hybridization between the Co and Ti atoms. The transport properties of these materials are discussed on the basis of Seebeck coefficients, electrical conductivity coefficients and thermal conductivity coefficients.     

Theoretical investigation of the crystallographic structure,anisotropic elastic response,and electronic properties of the major borides in Ni-based superalloys

ABSTRACT

In Ni-based superalloys, it is usually found that borides can strengthen the grain boundaries, thereby resulting in an increase in mechanical strength and high-temperature creep properties. Due to their importance and prevalence in Ni-based superalloys, this study employs first-principles methods to investigate the crystallographic structure, anisotropic elastic response, and electronic properties of the major borides, such as M₂B, M₅B₃ and M₃B₂ (M: Cr, Mo, W), respectively, which is necessary for the assessment of complex mechanical responses of Ni-based superalloys. The results demonstrate that the studied borides are all thermodynamically and mechanically stable. Among the M _x B _y binary borides analysed, Cr _x B _y exhibits the largest shear modulus, Young’s modulus, and Vicker hardness values, and these properties increase with the increase of B contents. The studied borides display nearly isotropic elastic properties except for W₅B₃ and W₃B₂. The electronic structure analysis of M _x B _y shows that the strong hybridisation between M-d and B-p orbitals leads to these borides exhibiting higher theoretical hardness, and the overlapping peaks of M-d and B-p orbitals move to a lower energy area with the increase of B contents, which leads to the increase of shear and Young’s moduli of M _x B _y . Furthermore, for M₃B₂ borides, the Cr-B bonds and Cr–Cr bonds are much stronger than the W-B & Mo-B bonds, and W-W & Mo-Mo bonds, respectively, which leads to Cr _x B _y yielding the largest values of elastic moduli.     

Structure,thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C _n mim⁺][Tf₂N^?] (n?=?4,?8,?12) ionic liquids (ILs) in a wide temperature range (298.15?498.15?K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.     

Structures and elastic properties of paraelectric and ferroelectric KTa0.5Nb0.5O3 from first-principles calculation

The structures, elastic properties and intrinsic hardness of B-O bonds of KTa_0.5Nb_0.5O₃ crystal in paraelectric and ferroelectric phase structures have been investigated by means of the density functional theory. Both structures are found to be elastically stable and in good agreement with available results. The elastic properties including the bulk modulus, shear modulus and Young’s modulus change largely during phase transition. The paraelectric KTa_0.5Nb_0.5O₃ crystal is more incompressible and harder than ferroelectric phase. The hardness of KTa_0.5Nb_0.5O₃ crystal is mostly determined by Nb-O bonds and the modifications of the bond strength affect the hardness of the crystal. Charge density contours indicate that the electronic distributions between B-O bonds play an important role in the formation of elastic properties.     

Symmetry coupling coefficients for the double groups C n*, D n* and T*

By coupling linear combinations of the |JM ket vectors which transform as irreducible representations of C_n *, D_n * and T*, symmetry coupling coefficients for these groups are calculated. Also, ? coefficients as defined by Golding [1] are evaluated.     

电光效应的自相似性

通过对KNbO₃,LiNbO₃,BaTiO₃及几种半导体晶体的电光系数进行数值分析，发现电光系数在自由状态和受夹状态下对应的Miller-δ系数相同，与外加电场频率无关，进而提出用Miller-δ系数表征晶体非线性光学性质.在此基础上，提出一种全新的电光效应产生机制，认为电光效应源于非线性系统的自相似性，表现为对线性性质的一种“自我复制”，而Miller-δ系数是“自我复制”的比例因子. 关键词： 电光效应 非线性光学 自相似性     

Intramolecular hydrogen bonds in the phenylazomethine biomolecules

The FTIR spectra of the solutions of biologically active molecules (screened phenylazomethines) in CCl₄ are studied. The role of the OH- and N=C groups in the formation of the intramolecular H bonds is analyzed. The analysis of the FTIR spectra shows that three types of H bonds (O-H…O-H, O-H…N=C, and O-H…O-H…N=C) are possible in the molecules under study. A correlation of the H-bond formation in the phenylazomethine molecules and the antivirus properties of such molecules is revealed. The antivirus activity is observed for molecules that exhibit intramolecular O-H…O-H…N=C bonds in the absence of free hydroxyls. The antivirus activity decreases when the molecule contains additional OH groups that are not involved in H bonds.     

Topological analysis of charge density in heptasulfur imide (S7NH) from isolated molecule to solid

Intra and intermolecular interactions of heptasulfur imide (S₇NH) are investigated in terms of topological properties analyses, such analyses are applied to both experimental (multipole model) and theoretically calculated (DFT and PDFT calculations) charge densities of the isolated molecule and of the crystal. The same analyses are also applied to a multipole model density obtained from theoretically (PDFT) derived structural amplitudes. The covalent bond character of S-N, N-H and S-S bonds are well described in terms of density, ρ_b, and total energy density, H_b, at the bond critical point r_c, though it is clear that the S-S bonds are weaker shared interactions than those of N-H and S-N bonds. Lone pair electron regions of sulfur and nitrogen atoms are revealed as the local charge concentration site from the Laplacian of charge density. The even weaker intermolecular interactions are well characterized; these include the N-H?S hydrogen bonding, N?S binding interactions and S?S binding interactions. All these intermolecular binding interactions are closed-shell interactions. The Laplacian of charge density demonstrates a directional intermolecular binding interaction. The corresponding intermolecular binding energies are derived by MP2/6-311+G(d,p) calculations. Atomic graph of each atom of the molecule is described in detail by the vertices, edges and faces of the polyhedron around the nucleus to illustrate such directional interactions.     

Growth mechanism of tantalum silicides by interdiffusion

Interdiffusion studies were conducted to understand the atomic mechanism of the diffusing species and the growth mechanism of the phases. Integrated diffusion coefficients and the ratio of tracer diffusion coefficients were estimated for these analyses. The activation energies for the integrated diffusion coefficients were calculated as 550?±?70 and 410?±?39?kJ/mol in the TaSi₂ and Ta₅Si₃ phases, respectively. In the TaSi₂ phase, Ta has a slightly lower but comparable diffusion rate with respect to Si, although no Ta–Ta bonds are present in the crystal. In the Ta₅Si₃ phase, Si has a higher diffusion rate, which is rather unusual, if we consider the atoms in the nearest-neighbour positions for both the elements. The ratio of Si to Ta tracer diffusion coefficients is found to be lower in the Si-rich phase, TaSi₂, compared to the Si-lean phase, Ta₅Si₃, which is also unusual. This indicates the type of structural defects present. An analysis on the growth mechanism of the phases indicates that duplex morphology and the Kirkendall marker plane should only be present in the TaSi₂ phase. This is not present in the Ta₅Si₃ phase due to the very high growth rate of the TaSi₂ phase, which consumes most of the Ta₅Si₃ phase layer. The problems in the calculation method used previously by others in this system are also explained.     

Structure of complexes of sulphuretted tetraphenylporphine with poly-N-vinylpyrrolidone according to the data of small-angle neutron scattering

Aqueous solutions of poly-N-vinylpirrolidone (PVP), a typical polymer for medical purposes, containing sulphuretted tetraphenylporphirine dihydrochloride (H₂TPPS₄(HCl)₂ or TPPS) having antiviral and therapeutic properties were studied. The association of PVP chains due to their nonvalent interactions with TPPS molecules playing the role of interchain and intrachain bonds was observed in complex solution over the temperature range from 20 to 90°C. The character of conformation changes of the polymer was determined; parameters of PVP binding with TPPS were calculated. The TPPS molecules were shown to be associated with PVP ones by means of hydrogen bonds between porphyrin sulfonic groups and polarized water molecules in the polymer hydration shell.