Calculating the energies for Ag(001) twist boundaries utilizing the modified analytical embedded atom method

The unrelaxed energies for Ag(001) twist grain boundaries (GBs) have been calculated using the modified analytical embedded atom method (MAEAM). The results show that, besides zero energy in a perfect crystal (corresponding to the twist angle 0°), the second smallest GB energy corresponds to the twist angle 36.87°. This is consistent with the experimental results. For other twist angles, the GB energies remain nearly constant even for a twist angle as small as 1.94°. Translation parallel to the boundary plane could result in a periodic change in GB energy. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of disorder in the twist angle on light scattering by a three-dimensional spherulite

Light scattering patterns are calculated for imperfect three-dimensional spherulites with fluctuations in the twist angle. The fluctuations are described in terms of a parameter characterizing the distance correlation function. Cases are considered in which (i) the principal axis of the scattering element makes a constant angle with the radius but there is disorder in the twist angle about the axis, and (ii) there is combined twist disorder and orientation disorder of the scattering elements. Calculations suggest that the disorder in the twist angle may lead to a decrease in the higher-order variation of scattered intensity with scattering angle and deviation from the four-leaf-clover-type scattering characteristic of a perfect spherulite at lower scattering angles. On the other hand, disorder in orientation has little effect on the scattering pattern.     

Influence of geometry on reductive elimination of hydrocarbyl-palladium-carbene complexes

The influence of spectator ligand bite angle and the twist angle of the carbene on the reductive elimination of N-heterocyclic carbenes (NHCs) from palladium bis-phosphine complexes has been investigated using density functional theory. The spectator bite angle was found to have a significant influence on both the activation energy (E(act)) and the enthalpy of reaction. Widening of the bite angle was found to lower E(act) and increase the enthalpy of reaction. In contrast, rotation of the carbene with respect to the PdL(2) plane was found to have little influence on E(act). At carbene twist angles approaching 0 degrees however, relief of the increased steric strain provides a considerable driving force for the decomposition reaction.     

Conformational and electronic engineering of twisted diphenylacetylenes

[structure: see text] Three tethered diphenylacetylene derivatives were prepared by alkyne metathesis. In these cycles, the twist angle between the two benzene rings is variable and determined by the nature of the linker. The engineering of the twist angle leads to a change of the UV-vis spectra of the cycles. The larger the twist angle in the macrocycles, the more blue shifted their lambda(max) (UV-vis), the lower their fluorescence quantum yield, and the lower field shifted their (13)C NMR signals of the alkyne carbons are.     

Smectic C* layer directional instabilities in cells with twist geometry

We have investigated the formation and structure of horizontal chevrons, as well as the reorientation dynamics of smectic layers under applied asymmetric electric fields in cells with a twist geometry. The tilted layer structure of horizontal chevron domains is found to be rotated by an angle approximately equal to the twist angle alpha, as compared with parallel rubbed substrates, alpha = 0°. The time of horizontal chevron formation decreases slightly with increasing twist angle. The smectic layer reorientation under application of time-asymmetric electric fields is found to be enhanced for reorientation into the direction of twist, while it is hindered for reorientation out of the direction of layer twist. Increasing the twist angle results in a basically linear increase/decrease in the reorientation velocity, depending on field asymmetry direction. The electro-optic behaviour of twist cells with inclined smectic layers is outlined and compared with measurements performed on cells with monostable, parallel anchoring conditions.     

Smectic C* layer directional instabilities in cells with twist geometry

We have investigated the formation and structure of horizontal chevrons, as well as the reorientation dynamics of smectic layers under applied asymmetric electric fields in cells with a twist geometry. The tilted layer structure of horizontal chevron domains is found to be rotated by an angle approximately equal to the twist angle alpha, as compared with parallel rubbed substrates, alpha = 0°. The time of horizontal chevron formation decreases slightly with increasing twist angle. The smectic layer reorientation under application of time-asymmetric electric fields is found to be enhanced for reorientation into the direction of twist, while it is hindered for reorientation out of the direction of layer twist. Increasing the twist angle results in a basically linear increase/decrease in the reorientation velocity, depending on field asymmetry direction. The electro-optic behaviour of twist cells with inclined smectic layers is outlined and compared with measurements performed on cells with monostable, parallel anchoring conditions.     

Modeling the nonradiative decay rate of electronically excited thioflavin T

A computational model of nonradiative decay is developed and applied to explain the time-dependent emission spectrum of thioflavin T (ThT). The computational model is based on a previous model developed by Glasbeek and co-workers (van der Meer, M. J.; Zhang, H.; Glasbeek, M. J. Chem. Phys. 2000, 112, 2878) for auramine O, a molecule that, like ThT, exhibits a high nonradiative rate. The nonradiative rates of both auramine O and ThT are inversely proportional to the solvent viscosity. The Glasbeek model assumes that the excited state consists of an adiabatic potential surface constructed by adiabatic coupling of emissive and dark states. For ThT, the twist angle between the benzothiazole and the aniline is responsible for the extensive mixing of the two excited states. At a twist angle of 90°, the S(1) state assumes a charge-transfer-state character with very small oscillator strength, which causes the emission intensity to be very small as well. In the ground state, the twist angle of ThT is rather small. The photoexcitation leads first to a strongly emissive state (small twist angle). As time progresses, the twist angle increases and the oscillator strength decreases. The fit of the experimental results by the model calculations is good for times longer than 3 ps. When a two-coordinate model is invoked or a solvation spectral-shift component is added, the fit to the experimental results is good at all times.     

含氮给体结构对丙烯腈电荷转移光聚合的影响

<正> 对于正性烯类单体,主要是乙烯基咔唑的电荷转移聚合,诚田已作过详细综述。负性烯类单体的电荷转移聚合主要研究的单体是丙烯腈(AN)及甲基丙烯酸甲酯(MMA)。Barton等研究了芳烃为引发剂的MMA光聚合。我们研究了芳胺为引发剂的光聚合。 芳胺,尤其是芳叔胺,是较强的电子给体,与负性单体在光照下经激基复合物而引发聚合,我们的实验表明,吡啶及其同系物(喹啉与吖啶)并不象吡咯及其同系物(吲哚与咔唑)那样有效地引发AN等负性单体的光聚合(见表1)。从图1所示的结构看,它们有     

Kinetic and computational study of dissociative substitution and phosphine exchange at tetrahedrally distorted cis-Pt(SiMePh2)2(PMe2Ph)2

The substitution kinetics of Me2PhP in cis-Pt(SiMePh2)2(PMe2Ph)2 (1) by the chelating ligand bis(diphenylphosphino)ethane has been followed at 25.0 degrees C in dichloromethane by stopped-flow spectrophotometry. Addition of the leaving ligand causes mass-law retardation compatible with a dissociative process via a three-coordinate transition state or intermediate. Exchange of Me2PhP in 1 has been studied by variable-temperature magnetization transfer 1H NMR in toluene-d8, giving kex326 = 1.76 +/- 0.12 s-1, delta H++ = 117.8 +/- 2.1 kJ mol-1, and delta S++ = 120 +/- 7 J K-1 mol-1. An exchange rate constant independent of the concentrations of free phosphine, a strongly positive delta S++, and nearly equal exchange and ligand dissociation rate constants also support a dissociative process. Density functional theory (DFT) calculations for a dissociative process give an estimate for the Pt-P bond energy of 98 kJ mol-1 for R = R' = Me, which is in reasonable agreement with the experimental activation energy given the differences between the substituents used in the calculation and those employed experimentally. DFT calculations on cis-Pt(PR3)2(SiR'3)2 (R = H, CH3; R' = H, CH3) are consistent with the experimental molecular structure and show that methyl substituents on the Si donors are sufficient to induce the observed tetrahedral twist. The optimized Si-Pt-Si angle in cis-Pt(SiH3)2(PH3)2 is not significantly altered by changing the P-Pt-P angle from its equilibrium value of 104 degrees to 80 degrees or 120 degrees. The origin of the tetrahedral twist is therefore not steric but electronic. The Si-Pt-Si angle is consistently less than 90 degrees, but the Si-Si distance is still too long to support an incipient reductive elimination reaction with its attendant Si-Si bonding interaction. Instead, it appears that four tertiary ligands introduce a steric strain which can be decreased by a twist of two of the ligands out of the plane; this twist is only possible when two strong sigma donors are cis to each other, causing a change in the metal's hybridization.     

Darstellung von tetraaryl-pyrrolen und vergleichende epr-g-faktor-untersuchung von pyrryl-radikalen mit tetracyclon-ketylen

The synthesis of a number of substituted tetraphenyl-pyrroles is presented. The electronic g-factors of the corresponding pyrryl radicals are measured by EPR techniques in solution. A linear relationship has been found between type and number of the substituents and the g-factor shift, Assuming a twist angle of 25° for the α- and 60° for the β-pheny] rings with respect to the plane of the five membered ring, the EPR data can be satisfactorily explained by means of HMO-McLachlan calculations. The twist angles of the phenyl rings in the analogous substituted tetracyclone-ketyl system which give the best fit to experiment are 65° for the α- and 20° for the β-phenyl rings, respectively. The different conformations found for the two systems can be explained by considering the different charge distributions in the pyrryl- and in the tetracyclone-ketyl-radicals.     

Twist viscosities and flow alignment of biaxial nematic liquid crystal phases of a soft ellipsoid-string fluid studied by molecular dynamics simulation

We have calculated the twist viscosity and the alignment angle between the director and the stream lines in shear flow of a liquid crystal model system, which forms biaxial nematic liquid crystals, as functions of the density, from the Green-Kubo relations by equilibrium molecular dynamics simulation and by a nonequilibrium molecular dynamics algorithm, where a torque conjugate to the director angular velocity is applied to rotate the director. The model system consists of a soft ellipsoid-string fluid where the ellipsoids interact according a repulsive version of the Gay-Berne potential. Four different length-to-width-to-breadth ratios have been studied. On compression, this system forms discotic or calamitic uniaxial nematic phases depending on the dimensions of the molecules, and on further compression a biaxial nematic phase is formed. In the uniaxial nematic phase there is one twist viscosity and one alignment angle. In the biaxial nematic phase there are three twist viscosities and three alignment angles corresponding to the rotation around the various directors and the different alignments of the directors relative to the stream lines, respectively. It is found that the smallest twist viscosity arises by rotation around the director formed by the long axes, the second smallest one arises by rotation around the director formed by the normals of the broadsides, and the largest one by rotation around the remaining director. The first twist viscosity is rather independent of the density whereas the last two ones increase strongly with density. One finds that there is one stable director alignment relative to the streamlines, namely where the director formed by the long axes is almost parallel to the stream lines and where the director formed by the normals of the broadsides is almost parallel to the shear plane. The relative magnitudes of the components of the twist viscosities span a fairly wide interval so this model should be useful for parameterisation experimental data.     

The conformations of bicyclo[3.1.0]hexane derivatives by 1H and 13C NMR

The ¹H and ¹³C spectra of bicyclo[3.1.0]hexanes and thujanes have been recorded and assigned. Application of the Karplus equation has yielded dihedral angles, and a computer calculation of the angle of ring buckle as a function of the main dihedral angles has been carried out. The calculated angles of ring buckle agree well with known values in the bicyclo[3.1.0]hexanes, but for 1-methylbicyclo[3.1.0]hexanes and thujanes the results are not self consistent. It is suggested that the bridgehead substituent causes the boat to twist, although the twist can be reduced by an axial methyl substituent on C-4.     

A numerical technique for predicting microstructure in liquid crystalline polymers

A numerical technique has been developed to model texture in nematic liquid crystals. The technique differentiates between splay, twist and bend distortions and includes splay-splay compensation. The technique is tested by the simulation of the Freedericksz transition and by the determination of minimum energy director fields for specific boundary conditions. To model the bulk, periodic boundary conditions are imposed. The effect of elastic anisotropy on disclination character has been investigated by terminating simulations before all the defects have been annihilated. With a low twist constant, twist disclinations are observed; with a high twist constant, wedge disclinations are observed. With a low twist constant and high splay constant, realistic for polymeric liquid crystals, features observed experimentally are simulated.     

Synthesis and characterization of tetrakis(2,6-diethylphenyl)digermene

Tetrakis(2,6-diethylphenyl)digermene (1b) has been synthesized and its molecular structure determined: (1) the GeGe bond length is 2.213(2) Å and (2) the molecule has a twist angle of 11° about the GeGe bond and an out-of-plane bending angle of 15° at the germanium atoms.     

A theoretical study on the specific interaction of hexafluorobenzene with benzene and p -xylene

A cndo/2 study has been carried out for C₆F₆ + C₆H₆aad C₆F₆ + C₆H₁₀ composites and individual molecules. The favoured configurations of the adducts have been decided on the basis of energy calculations of various geometries. For the C₆F₆+C₆H₆ adduct the lowest energy corresponds to the configuration in which the molecular planes are parallel to each other with a twist angle of 30°. For the C₆F₆+ C₈H₁₀ adduct lowest energy corresponds to a geometry in which the two molecular planes are inclined by a small angle with the angle of twist between the molecular planes being 30°. It is shown that the complexes are not of the charge transfer type.     

Structural variations across the lanthanide series of macrocyclic DOTA complexes: insights into the design of contrast agents for magnetic resonance imaging

It was early shown that the macrocyclic Ln(DOTA) complexes (DOTA = 1,4,7,10-tetra-azacyclododecane-N,N',N' ',N' "-tetraacetic acid) exists in solution as a mixture of two enantiomeric pairs of diastereoisomers differing in the ligand conformation, namely, square antiprismatic (SA) and twisted square antiprismatic (TSA) geometries, respectively. Later, extensive (1)H NMR investigations suggested that a coordination change may be superimposed on this conformational equilibrium involving two additional structures in which the metal ion possesses a coordination number of eight (CN 8). It was predicted that these two species, lacking the apical coordinated water molecule, would maintain the SA and TSA coordination geometries, and therefore, they have been labeled as SA' and TSA', respectively. In this work we report the X-ray solid-state crystal structure determination of six Ln(DOTA) complexes representative of all four coordination geometry typologies deduced from NMR solution studies. A distinctive structural feature that discriminates SA (and SA') and TSA (and TSA') structures is represented by the twist angle between the two square planes of the antiprism, the basal four nitrogen, and the apical four oxygen planes. [Ce(DOTA)(H(2)O)](-) displays a TSA structural typology with a twist angle of 25 degrees and a Ce-O(water) distance of 2.59 A. The SA-type structure has been found in the case of complexes with Pr(III), Nd(III), and Dy(III), where the twist angle is 39, 39, and 38 degrees, respectively, and the metal-water oxygen distance varies significantly (Pr-O(w) 2.529 A; Nd-O(w) 2.508 A; and Dy-O(w) 2.474 A). [Tm(DOTA)](-) displays a TSA'-type structure with a twist angle of 24 degrees. As compared with the TSA structure of the corresponding Ce(III) complex, the Tm(III) complex shows an overall marked shrinkage of all metal-nitrogen and metal-oxygen distances (ca. 0.2 A), which reflects the contraction of the metal ionic radius across the series but also the effect associated with the decrease of the CN from 9 to 8. In [Sc(DOTA)](-), the even smaller ionic radius of Sc(III) shifts the geometry of the coordination cage to the more compact SA' typology with a twist angle of 41 degrees, a value very similar to that found in the SA structures of lanthanide(III) ions with CN 9. Finally, an investigation was made into the hydration spheres of the complexes with SA and TSA geometries to account for the experimental evidence of a markedly different rate of water exchange for the two isomeric structures. This is of fundamental importance to the understanding of the corresponding Gd(III) complexes as MRI contrast agents.     

Measurement of twist angle and surface torsional anchoring strength in a nematic liquid crystal cell

In this paper a novel method is developed for measuring the twist angle and surface torsional anchoring strength in nematic liquid crystal (NLC) cells. This method is based on a technique developed from the Jones optical propagation matrix. From the measurement, the actual twist angle in NLC cell and the deviation of the LC director on the boundary of the cell from the rubbing direction of the substrate are obtained. A theoretical discussion shows that the surface torsional anchoring strength has a great influence on the value of the deviation, and hence so it can be calculated.     

Quantification of the azimuthal anchoring of a homogeneously aligned nematic liquid crystal using fully-leaky guided modes

A novel optical guided mode technique, the fully-leaky guided mode technique, has been used to investigate the director distortion under the application of an in-plane electric field of a homogeneously aligned conventional cell filled with the nematic liquid crystal E7. The liquid crystal is aligned using polyimide rubbed along the direction of the gold electrode edges. A weak field is applied across a 3 mm gap between the gold electrodes to induce small changes in the twist angle of the director. These distortions are determined by fitting to the angledependent reflectivity and transmissivity data and are compared with continuum theory. From careful analysis of the results, both the twist elastic constant, k22, and the azimuthal anchoring strength, Wa, of the system are obtained. At 23.5 C for E7 on rubbed polyimide we find that k22=(6.50 +/- 0.05)x10-12N and Wa=(2.9 +/- 0.2)x10-5 J m-2.     

Thermodynamics of twisted DNA with solvent interaction

The imaginary time path integral formalism is applied to a nonlinear Hamiltonian for a short fragment of heterogeneous DNA with a stabilizing solvent interaction term. Torsional effects are modeled by a twist angle between neighboring base pairs stacked along the molecule backbone. The base pair displacements are described by an ensemble of temperature dependent paths thus incorporating those fluctuational effects which shape the multisteps thermal denaturation. By summing over ~10(7)-10(8) base pair paths, a large number of double helix configurations is taken into account consistently with the physical requirements of the model potential. The partition function is computed as a function of the twist. It is found that the equilibrium twist angle, peculiar of B-DNA at room temperature, yields the stablest helicoidal geometry against thermal disruption of the base pair hydrogen bonds. This result is corroborated by the computation of thermodynamical properties such as fractions of open base pairs and specific heat.     

Electronic structures and properties of twisted polyacenes

The effects of twisting on the electronic structures and properties of polyacenes were studied computationally using DFT methods. Singlet-triplet and HOMO-LUMO gaps and vertical S0-S1 transition energies are marginally affected as a function of end-to-end twist angle. The large twist induced by the phenyl substituents in 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene has little influence on its electronic structure.