NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

Schlieren visualization of shock wave phenomena over a missile-shaped body at hypersonic Mach numbers

The flow over a missile-shaped configuration is investigated by means of Schlieren visualization in short-duration facility producing free stream Mach numbers of 5.75 and 8. This visualization technique is demonstrated with a 41 degrees full apex angle blunt cone missile-shaped body mounted with and without cavity. Experiments are carried out with air as the test gas to visualize the flow field. The experimental results show a strong intensity variation in the deflection of light in a flow field, due to the flow compressibility. Shock stand-off distance measured with the Schlieren method is in good agreement with theory and computational fluid dynamic study for both the configurations. Magnitude of the shock oscillation for a cavity model may be greater than the case of a model without cavity. The picture of visualization shows that there is an outgoing and incoming flow closer to the cavity. Cavity flow oscillation was found to subside to steady flow with a decrease in the free stream Mach number.

Piezoelectrically actuated insect scale flapping wing

An energy method is used in order to derive the non-linear equations of motion of a smart flapping wing. Flapping wing is actuated from the root by a PZT unimorph in the piezofan configuration. Dynamic characteristics of the wing, having the same size as dragonfly Aeshna Multicolor, are analyzed using numerical simulations. It is shown that flapping angle variations of the smart flapping wing are similar to the actual dragonfly wing for a specific feasible voltage. An unsteady aerodynamic model based on modified strip theory is used to obtain the aerodynamic forces. It is found that the smart wing generates sufficient lift to support its own weight and carry a small payload. It is therefore a potential candidate for flapping wing of micro air vehicles.

Quantum Properties in Transport Through Nanoscopic Rings:Charge-Spin Separation and Interference Effects

Many of the most intriguing quantum effects are observed or could be measured in transport experiments through nanoscopic systems such as quantum dots, wires and rings formed by large molecules or arrays of quantum dots. In particular, the separation of charge and spin degrees of freedom and interference effects have important consequences in the conductivity through these systems. Charge-spin separation was predicted theoretically in one-dimensional strongly inter-acting systems (Luttinger liquids) and, although observed indirectly in several materials formed by chains of correlated electrons, it still lacks direct observation. We present results on transport properties through Aharonov-Bohmrings (pierced by a magnetic flux) with one or more channels represented by paradigmatic strongly-correlated models. For a wide range of parameters we observe characteristic dips in the conductance as a function of magnetic flux which are a signature of spin and charge separation. Interference effects could also be controlled in certain molecules and interesting properties could be observed. We analyze transport properties of conjugated molecules, benzene in particular, and find that the conductance depends on the lead configuration. In molecules with translational symmetry, the conductance can be controlled by breaking or restoring this symmetry, e.g. by the application of a local external potential. These results open the possibility of observing these peculiar physical properties in anisotropic ladder systems and in real nanoscopic and molecular devices.

Thermodynamic Study of Mixed Anionic Solid Solutions Using Gradient Solid Electrolytes System K2CO3 - K2SO4

The thermodynamic properties of K2CO3 -KSO, solid solutions with hexagonal structure have been measured using a solid-state cell, incorporating a composite solid electrolyte with step-changes in composition. The cell with the configuration Pt, CO2' + O2' || K2CO3 | K2(CO3)x(SO4)1-x || CO2'' + O2'' + Pt X =1 X=X was investigated in the temperature range of 925 to 1165 K. The composite gradient solid electrolyte consisted of pure K2CO3 at one extremity and the solid solution under study at the other. The Nernstian response of the cell to changes in partial pressures of CO2 and O2 at the electrodes and temperature was demonstrated. The activity of K2CO3 in the solid solution was measured by three techniques. All three methods gave identical results, indicating unit transport number for K+ ions and negligible diffusion potential due to concentration gradients of carbonate and sulfate ions. The activity of K2CO3 exhibits positive deviation from Raoult's law. The excess Gibbs energy of mixing of the solid solution can be represented using a subregular solution model DELTAG(E) = X(1 - X)[5030X + 4715(1 - X)] J mol-1 By combining this information with the phase diagram, mixing properties of the liquid phase were obtained.

Thermomechanical behaviour of pin joints subjected to sheet loads

An important problem regarding pin joints in a thermal environment is addressed. The motivation emerges from structural safety requirements in nuclear and aerospace engineering. A two-dimensional model of a smooth, rigid misfit pin in a large isotropic sheet is considered as an abstraction. The sheet is subjected to a biaxial stress system and far-field unidirectional heat flow. The thermoelastic analysis is complex due to non-linear load-dependent contact and separation conditions at the pin-hole interface and the absence of existence and uniqueness theorems for the class of frictionless thermoelastic contact problems. Identification of relevant parameters and appropriate synthesis of thermal and mechanical variables enables the thermomechanical generalization of pin-joint behaviour. This paper then proceeds to explore the possibility of multiple solutions in such problems, especially interface contact configuration.

Enantiospecific synthesis and confirmation of the relative and absolute stereostructure of 11-hydroxyguaiadienes

Enantiospecific total synthesis of two epimeric sesquiterpenes 11-hydroxyguaiadienes has been accomplished starting from the readily available monoterpene (R)-limonene, which confirmed the structure and absolute configuration of the natural products. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis, Reactivity, Structural Aspects, and Solution Dynamics of Cyclopalladated Compounds of N,N `,N `'-Tris(2-anisyl)guanidine

N,N',N `'-Tris(2-anisyl)guanidine, (ArNH)(2)C=NAr (Ar = 2-(MeO)C6H4), was cyclopallaclated with Pd(OC(O)R)(2) (R = Me, CF3) in toluene at 70 degrees C to afford palladacycles Pd{kappa(2)(C,N)-C6H3-(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-OC(O)R)](2)(R = Me (1a) and CF3 (1b)) in 87% and 95% yield, respectively. Palladacycle 1a was subjected to a metathetical reaction with LiBr in aqueous ethanol at 78 degrees C to afford palladacycle Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (2) in 90% yield. Palladacycle 2 was subjected to a bridge-splitting reaction with Lewis bases in CH2Cl2 to afford the monomeric palladacycles Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}Br(L)] (L = 2,6-Me2C5H3N (3a), 2,4-Me2C5H3N (3b), 3,5-Me2C5H3N (3c), XyNC (Xy = 2,6-Me2C6H3; 4a), (BuNC)-Bu-t (4b), and PPh3 (5)) in 87-95% yield. Palladacycle 2 upon reaction with 2 equiv of XyNC in CH2Cl2 afforded an unanticipated palladacycle, Pd{kappa(2)(C,N)-C(=NXy)(C6H3(OMe)-4)-2(N=C-(NH Ar)(2))-3} Br(CNXy)] (6) in 93% yield, and the driving force for the formation of 6 was ascribed to a ring contraction followed by amine-imine tautomerization. Palladacycles 1 a,b revealed a dimeric transoid in-in conformation with ``open book'' framework in the solid state. In solution, 1 a exhibited a fluxional behavior ascribed to the six-membered ``(C,N)Pd'' ring inversion and partly dissociates to the pincer type and kappa(2)-O,O'-OAc monomeric palladacycles by an anchimerically assisted acetate cleavage process as studied by variable-temperature H-1 NMR data. Palladacycles 3a,b revealed a unique trans configuration around the palladium with lutidine being placed trans to the Pd-C bond, whereas cis stereochemistry was observed between the Pd-C bond and the Lewis base in 4a (as determined by X-ray diffraction data) and 5 (as determined by P-31 and C-13 NMR data). The aforementioned stereochemical difference was explained by invoking relative hardness/softness of the donor atoms around the palladium center. In solution, palladacycles 3a-c exist as a mixture of two interconverting boat conformers via a planar intermediate without any bond breaking due to the six-membered ``(C,N)Pd'' ring inversion, whereas palladacycles 4a,b and 5 exist as a single isomer, as deduced from detailed H-1 NMR studies.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

Geometry and quadratic nonlinearity of charge transfer complexes in solution: A theoretical study

In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO/S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, beta(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases. (C) 2011 American Institute of Physics. doi:10.1063/1.3526748]

Parallel Tempering Simulations of Liquid-Phase Adsorption of n-Alkane Mixtures in Zeolite LTA-5A

Adsorption of n-alkane mixtures in the zeolite LTA-5A under liquid-phase conditions has been studied using grand canonical Monte Carlo (GCMC) simulations combined with parallel tempering. Normal GCMC techniques fail for some of these systems due to the preference of linear molecules to coil within a single cage in the zeolite. The narrow zeolite windows severerly restrict interactions of the molecules, making it difficult to simulate cooperative rearrangements necessary to explore configuration space. Because of these reasons, normal GCMC simulations results show poor reproducibility in some cases. These problems were overcome with parallel tempering techniques. Even with parallel tempering, these are very challenging systems for molecular simulation. Similar problems may arise for other zeolites such as CHA, AFX, ERI, KFI, and RHO having cages connected by narrow windows. The simulations capture the complex selectivity behavior observed in experiments such as selectivity inversion and azeotrope formation.

A discrete state perspective of manipulator workspaces Vorstellungen von diskreten zuständen von manipulator-arbeitsräumen

The finite resolution of joint drives or sensors imparts a discrete nature to the joints of a manipulator. Because of this an arbitrary point in the workspace cannot be reached without error even in ideal mechanical environment. This paper investigates the effect of this discrete nature of the joints on the accuracy of performance of a manipulator and develops a method to select the joint states to reach a point with least error. It is shown that the configuration leading to least error cannot, in general, be found from configuration space, especially when there is large variation in the link lengths or joint resolutions or both. The anomaly becomes severe when the gross motion of the end-effector approaches the local resolution of the workspace. The paper also shows how to distinguish two workspaces which may be identical so far as the boundary points are concerned, taking the joint resolutions into account. Finally, the concepts have been extended to define continuous space global and local performance indices for general multi degree of freedom manipulators.

A general procedure for modified crack closure integral in 3D problems with cracks

In linear elastic fracture mechanics (LEFM), Irwin's crack closure integral (CCI) is one of the signficant concepts for the estimation of strain energy release rates (SERR) G, in individual as well as mixed-mode configurations. For effective utilization of this concept in conjunction with the finite element method (FEM), Rybicki and Kanninen [Engng Fracture Mech. 9, 931 938 (1977)] have proposed simple and direct estimations of the CCI in terms of nodal forces and displacements in the elements forming the crack tip from a single finite element analysis instead of the conventional two configuration analyses. These modified CCI (MCCI) expressions are basically element dependent. A systematic derivation of these expressions using element stress and displacement distributions is required. In the present work, a general procedure is given for the derivation of MCCI expressions in 3D problems with cracks. Further, a concept of sub-area integration is proposed which facilitates evaluation of SERR at a large number of points along the crack front without refining the finite element mesh. Numerical data are presented for two standard problems, a thick centre-cracked tension specimen and a semi-elliptical surface crack in a thick slab. Estimates for the stress intensity factor based on MCCI expressions corresponding to eight-noded brick elements are obtained and compared with available results in the literature.

An examination of the BEBO model with the results of ab initio calculations of a reaction series

The BEBO (bond energy-bond order) model of Johnston and Parr is examined with the results of ab initio MO calculations on a series of metathetic reactions which involve hydrogen transfer. Energies are calculated at the 6-31G**/PMP2 = full//6-31G** level while the bond orders are estimated using the 6-31G** basis set with the geometry optimisation at the single configuration unrestricted Hartree-Fock frame. Our analysis reveals that the bond-order exponent in the BEBO theory is greater than unity for the reaction series and the entropy term becomes implicitly present in the BEBO model.

Barrier crossing in one and three dimensions by a long chain

We consider the Kramers problem for a long chain polymer trapped in a biased double-well potential. Initially the polymer is in the less stable well and it can escape from this well to the other well by the motion of its N beads across the barrier to attain the configuration having lower free energy. In one dimension we simulate the crossing and show that the results are in agreement with the kink mechanism suggested earlier. In three dimensions, it has not been possible to get an analytical `kink solution' for an arbitrary potential; however, one can assume the form of the solution of the nonlinear equation as a kink solution and then find a double-well potential in three dimensions. To verify the kink mechanism, simulations of the dynamics of a discrete Rouse polymer model in a double well in three dimensions are carried out. We find that the time of crossing is proportional to the chain length, which is in agreement with the results for the kink mechanism. The shape of the kink solution is also in agreement with the analytical solution in both one and three dimensions.