Fe as Hydrogen/Halogen Bond Acceptor in Square Pyramidal Fe(CO)(5)

Hydrogen bonded complexes formed between the square pyramidal Fe(CO)(5) with HX (X = F, Cl, Br), showing X-H center dot center dot center dot Fe interactions, have been investigated theoretically using density functional theory (DFT) including dispersion correction. Geometry, interaction energy, and large red shift of about 400 cm(-1) in the FIX stretching frequency confirm X-H center dot center dot center dot Fe hydrogen bond formation. In the (CO)(5)Fe center dot center dot center dot HBr complex, following the significant red shift, the HBr stretching mode is coupled with the carbonyl stretching modes. This clearly affects the correlation between frequency shift and binding energy, which is a hallmark of hydrogen bonds. Atoms in Molecule (AIM) theoretical analyses show the presence of a bond critical point between the iron and the hydrogen of FIX and significant mutual penetration. These X-H center dot center dot center dot Fe hydrogen bonds follow most but not all of the eight criteria proposed by Koch and Popelier (J. Phys. Chem. 1995, 99, 9747) based on their investigations on C-H center dot center dot center dot O hydrogen bonds. Natural bond orbital (NBO) analysis indicates charge transfer from the organometallic system to the hydrogen bond donor. However, there is no correlation between the extent of charge transfer and interaction,energy, contrary to what is proposed in the recent IUPAC recommendation (Pure Appl.. Chem. 2011, 83, 1637). The ``hydrogen bond radius'' for iron has been determined to be 1.60 +/- 0.02 angstrom, and not surprisingly it is between the covalent (127 angstrom) and van der Waals (2.0) radii of Fe. DFT and AIM theoretical studies reveal that Fe in square pyramidal Fe(CO)(5) can also form halogen bond with CIF and ClH as ``halogen bond donor''. Both these complexes show mutual penetration as well, though the Fe center dot center dot center dot Cl distance is closer to the sum of van der Waals radii of Fe and Cl in (CO)5Fe center dot center dot center dot ClH, and it is about 1 angstrom less in (CO)(5)Fe center dot center dot center dot ClF.

Terminal Impact Angle Constrained Guidance Laws Using Variable Structure Systems Theory

In this brief, variable structure systems theory based guidance laws, to intercept maneuvering targets at a desired impact angle, are presented. Choosing the missile's lateral acceleration (latax) to enforce sliding mode, which is the principal operating mode of variable structure systems, on a switching surface defined by the line-of-sight angle leads to a guidance law that allows the achievement of the desired terminal impact angle. As will be shown, this law does not ensure interception for all states of the missile and the target during the engagement. Hence, additional switching surfaces are designed and a switching logic is developed that allows the latax to switch between enforcing sliding mode on one of these surfaces so that the target can be intercepted at the desired impact angle. The guidance laws are designed using nonlinear engagement dynamics for the general case of a maneuvering target.

Sustaining cooperation on networks: an analytical study based on evolutionary game theory

We analytically study the role played by the network topology in sustaining cooperation in a society of myopic agents in an evolutionary setting. In our model, each agent plays the Prisoner's Dilemma (PD) game with its neighbors, as specified by a network. Cooperation is the incumbent strategy, whereas defectors are the mutants. Starting with a population of cooperators, some agents are switched to defection. The agents then play the PD game with their neighbors and compute their fitness. After this, an evolutionary rule, or imitation dynamic is used to update the agent strategy. A defector switches back to cooperation if it has a cooperator neighbor with higher fitness. The network is said to sustain cooperation if almost all defectors switch to cooperation. Earlier work on the sustenance of cooperation has largely consisted of simulation studies, and we seek to complement this body of work by providing analytical insight for the same. We find that in order to sustain cooperation, a network should satisfy some properties such as small average diameter, densification, and irregularity. Real-world networks have been empirically shown to exhibit these properties, and are thus candidates for the sustenance of cooperation. We also analyze some specific graphs to determine whether or not they sustain cooperation. In particular, we find that scale-free graphs belonging to a certain family sustain cooperation, whereas Erdos-Renyi random graphs do not. To the best of our knowledge, ours is the first analytical attempt to determine which networks sustain cooperation in a population of myopic agents in an evolutionary setting.

Energy Hyperspace for Stacking Interaction in AU/AU Dinucleotide Step: Dispersion-Corrected Density Functional Theory Study

Double helical structures of DNA and RNA are mostly determined by base pair stacking interactions, which give them the base sequence-directed features, such as small roll values for the purine-pyrimidine steps. Earlier attempts to characterize stacking interactions were mostly restricted to calculations on fiber diffraction geometries or optimized structure using ab initio calculations lacking variation in geometry to comment on rather unusual large roll values observed in AU/AU base pair step in crystal structures of RNA double helices. We have generated stacking energy hyperspace by modeling geometries with variations along the important degrees of freedom, roll, and slide, which were chosen via statistical analysis as maximally sequence dependent. Corresponding energy contours were constructed by several quantum chemical methods including dispersion corrections. This analysis established the most suitable methods for stacked base pair systems despite the limitation imparted by number of atom in a base pair step to employ very high level of theory. All the methods predict negative roll value and near-zero slide to be most favorable for the purine-pyrimidine steps, in agreement with Calladine's steric clash based rule. Successive base pairs in RNA are always linked by sugar-phosphate backbone with C3-endo sugars and this demands C1-C1 distance of about 5.4 angstrom along the chains. Consideration of an energy penalty term for deviation of C1-C1 distance from the mean value, to the recent DFT-D functionals, specifically B97X-D appears to predict reliable energy contour for AU/AU step. Such distance-based penalty improves energy contours for the other purine-pyrimidine sequences also. (c) 2013 Wiley Periodicals, Inc. Biopolymers 101: 107-120, 2014.

MRT Letter: Experimental Verification of Vectorial Theory to Determine Field at the Geometrical Focus of a Cylindrical Lens

We provide experimental evidence supporting the vectorial theory for determining electric field at and near the geometrical focus of a cylindrical lens. This theory provides precise distribution of field and its polarization effects. Experimental results show a close match (approximate to 95% using (2)-test) with the simulation results (obtained using vectorial theory). Light-sheet generated both at low and high NA cylindrical lens shows the importance of vectorial theory for further development of light-sheet techniques. Potential applications are in planar imaging systems (such as, SPIM, IML-SPIM, imaging cytometry) and spectroscopy. Microsc. Res. Tech. 77:105-109, 2014. (c) 2014 Wiley Periodicals, Inc.

Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile

FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The C-13 nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital (GIAO) method and compared with experimental results. Standard thermodynamic functions have been obtained and changes in thermodynamic properties on going from monomer to tetramer have been presented. (C) 2013 Elsevier B.V. All rights reserved.

Electronic structure of Nd1-xYxMnO3 from Mn K edge absorption spectroscopy and DFT methods

The electronic structure of Nd1-xYxMnO3 (x-0-0.5) is studied using x-ray absorption near-edge structure (XANES) spectroscopy at the Mn K-edge along with the DFT-based LSDA+U and real space cluster calculations. The main edge of the spectra does not show any variation with doping. The pre-edge shows two distinct features which appear well-separated with doping. The intensity of the pre-edge decreases with doping. The theoretical XANES were calculated using real space multiple scattering methods which reproduces the entire experimental spectra at the main edge as well as the pre-edge. Density functional theory calculations are used to obtain the Mn 4p, Mn 3d and O 2p density of states. For x=0, the site-projected density of states at 1.7 eV above Fermi energy shows a singular peak of unoccupied e(g) (spin-up) states which is hybridized Mn 4p and O 2p states. For x=0.5, this feature develops at a higher energy and is highly delocalized and overlaps with the 3d spin-down states which changes the pre-edge intensity. The Mn 4p DOS for both compositions, show considerable difference between the individual p(x), p(y) and p(z)), states. For x=0.5, there is a considerable change in the 4p orbital polarization suggesting changes in the Jahn-Teller effect with doping. (C) 2013 Elsevier Ltd. All rights reserved.

Simulation of inhomogeneous distributions of ultracold atoms in an optical lattice via a massively parallel implementation of nonequilibrium strong-coupling perturbation theory

We present a nonequilibrium strong-coupling approach to inhomogeneous systems of ultracold atoms in optical lattices. We demonstrate its application to the Mott-insulating phase of a two-dimensional Fermi-Hubbard model in the presence of a trap potential. Since the theory is formulated self-consistently, the numerical implementation relies on a massively parallel evaluation of the self-energy and the Green's function at each lattice site, employing thousands of CPUs. While the computation of the self-energy is straightforward to parallelize, the evaluation of the Green's function requires the inversion of a large sparse 10(d) x 10(d) matrix, with d > 6. As a crucial ingredient, our solution heavily relies on the smallness of the hopping as compared to the interaction strength and yields a widely scalable realization of a rapidly converging iterative algorithm which evaluates all elements of the Green's function. Results are validated by comparing with the homogeneous case via the local-density approximation. These calculations also show that the local-density approximation is valid in nonequilibrium setups without mass transport.

Copula-Based Modeling of TMI Brightness Temperature With Rainfall Type

Overland rain retrieval using spaceborne microwave radiometer offers a myriad of complications as land presents itself as a radiometrically warm and highly variable background. Hence, land rainfall algorithms of the Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) have traditionally incorporated empirical relations of microwave brightness temperature (Tb) with rain rate, rather than relying on physically based radiative transfer modeling of rainfall (as implemented in the TMI ocean algorithm). In this paper, sensitivity analysis is conducted using the Spearman rank correlation coefficient as benchmark, to estimate the best combination of TMI low-frequency channels that are highly sensitive to the near surface rainfall rate from the TRMM Precipitation Radar (PR). Results indicate that the TMI channel combinations not only contain information about rainfall wherein liquid water drops are the dominant hydrometeors but also aid in surface noise reduction over a predominantly vegetative land surface background. Furthermore, the variations of rainfall signature in these channel combinations are not understood properly due to their inherent uncertainties and highly nonlinear relationship with rainfall. Copula theory is a powerful tool to characterize the dependence between complex hydrological variables as well as aid in uncertainty modeling by ensemble generation. Hence, this paper proposes a regional model using Archimedean copulas, to study the dependence of TMI channel combinations with respect to precipitation, over the land regions of Mahanadi basin, India, using version 7 orbital data from the passive and active sensors on board TRMM, namely, TMI and PR. Studies conducted for different rainfall regimes over the study area show the suitability of Clayton and Gumbel copulas for modeling convective and stratiform rainfall types for the majority of the intraseasonal months. Furthermore, large ensembles of TMI Tb (from the most sensitive TMI channel combination) were generated conditional on various quantiles (25th, 50th, 75th, and 95th) of the convective and the stratiform rainfall. Comparatively greater ambiguity was observed to model extreme values of the convective rain type. Finally, the efficiency of the proposed model was tested by comparing the results with traditionally employed linear and quadratic models. Results reveal the superior performance of the proposed copula-based technique.

Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone-Wales defects to show the largest enhancement with respect to pristine graphene (similar to 20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO2 and CH4 are, similar, although CO2 binding is generally stronger by similar to 4 to 5 kJ mol(-1). However, the differential between the adsorption of CO2 and CH4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH4/CO2 flow separation and gasselective sensors.

Anomalous power law decay in solvation dynamics of DNA: a mode coupling theory analysis of ion contribution

Several time dependent fluorescence Stokes shift (TDFSS) experiments have reported a slow power law decay in the hydration dynamics of a DNA molecule. Such a power law has neither been observed in computer simulations nor in some other TDFSS experiments. Here we observe that a slow decay may originate from collective ion contribution because in experiments DNA is immersed in a buffer solution, and also from groove bound water and lastly from DNA dynamics itself. In this work we first express the solvation time correlation function in terms of dynamic structure factors of the solution. We use mode coupling theory to calculate analytically the time dependence of collective ionic contribution. A power law decay in seen to originate from an interplay between long-range probe-ion direct correlation function and ion-ion dynamic structure factor. Although the power law decay is reminiscent of Debye-Falkenhagen effect, yet solvation dynamics is dominated by ion atmosphere relaxation times at longer length scales (small wave number) than in electrolyte friction. We further discuss why this power law may not originate from water motions which have been computed by molecular dynamics simulations. Finally, we propose several experiments to check the prediction of the present theoretical work.

Spectral finite element based on an efficient layerwise theory for wave propagation analysis of composite and sandwich beams

In this paper, we present a spectral finite element model (SFEM) using an efficient and accurate layerwise (zigzag) theory, which is applicable for wave propagation analysis of highly inhomogeneous laminated composite and sandwich beams. The theory assumes a layerwise linear variation superimposed with a global third-order variation across the thickness for the axial displacement. The conditions of zero transverse shear stress at the top and bottom and its continuity at the layer interfaces are subsequently enforced to make the number of primary unknowns independent of the number of layers, thereby making the theory as efficient as the first-order shear deformation theory (FSDT). The spectral element developed is validated by comparing the present results with those available in the literature. A comparison of the natural frequencies of simply supported composite and sandwich beams obtained by the present spectral element with the exact two-dimensional elasticity and FSDT solutions reveals that the FSDT yields highly inaccurate results for the inhomogeneous sandwich beams and thick composite beams, whereas the present element based on the zigzag theory agrees very well with the exact elasticity solution for both thick and thin, composite and sandwich beams. A significant deviation in the dispersion relations obtained using the accurate zigzag theory and the FSDT is also observed for composite beams at high frequencies. It is shown that the pure shear rotation mode remains always evanescent, contrary to what has been reported earlier. The SFEM is subsequently used to study wavenumber dispersion, free vibration and wave propagation time history in soft-core sandwich beams with composite faces for the first time in the literature. (C) 2014 Elsevier Ltd. All rights reserved.

New 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles: synthesis, liquid crystalline behavior and photo physical properties

A new series of luminescent 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles containing three ring systems, viz. methoxy pyridine, benzonitrile and alkoxy benzene with variable alkoxy chain length, with bent-core structures were synthesized as potential mesogens and characterized by spectral techniques. Their liquid crystalline behavior was investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and variable temperature powder X-ray diffraction (PXRD) measurements. The study reveals that compounds with shorter chain lengths i.e. m = 4] exclusively exhibit the nematic phase while compounds with longer chain lengths i.e. m = 6-14 (only even)] show predominantly the orthorhombic columnar phase. Single crystal X-ray analysis of 4-(2-(4-butyloxy/octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitriles reveals that they possess slightly non-planar unsymmetrical bent structures and their molecular packing consists of nonconventional H-bond interactions; it also explains the observed liquid crystalline phase. An optical study indicates that the title compounds are good blue emitting materials showing absorption and emission bands in the range 335-345 nm and 415-460 nm, respectively. An electrochemical study of 4-(2-(4-octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitrile shows a band gap of 1.89 eV with HOMO and LUMO energy levels of -5.06 and -3.17 eV, respectively. Also, density functional theory (DFT) calculations confirm its optimized geometry, electronic absorption and frontier molecular orbital distributions.

Orbital phase resolved spectroscopy of GX 301-2 with MAXI

GX 301-2, a bright high-mass X-ray binary with an orbital period of 41.5 d, exhibits stable periodic orbital intensity modulations with a strong pre-periastron X-ray flare. Several models have been proposed to explain the accretion at different orbital phases, invoking accretion via stellar wind, equatorial disc, and accretion stream from the companion star. We present results from exhaustive orbital phase resolved spectroscopic measurements of GX 301-2 using data from the Gas Slit Camera onboard MAXI. Using spectroscopic analysis of the MAXI data with unprecedented orbital coverage for many orbits continuously, we have found a strong orbital dependence of the absorption column density and equivalent width of the iron emission line. A very large equivalent width of the iron line along with a small value of the column density in the orbital phase range 0.10-0.30 after the periastron passage indicates the presence of high density absorbing matter behind the neutron star in this orbital phase range. A low energy excess is also found in the spectrum at orbital phases around the pre-periastron X-ray flare. The orbital dependence of these parameters are then used to examine the various models about mode of accretion on to the neutron star in GX 301-2.