Study of molecular reorientation and quantum rotational tunneling in tetramethylammonium selenate by H-1 NMR

H-1 NMR spin-lattice relaxation time measurements have been carried out in [(CH3)(4)N](2)SeO4 in the temperature range 389-6.6K to understand the possible phase transitions, internal motions and quantum rotational tunneling. A broad T, minimum observed around 280K is attributed to the simultaneous motions of CH3 and (CH3)(4)N groups. Magnetization recovery is found to be stretched exponential below 72 K with varying stretched exponent. Low-temperature T-1 behavior is interpreted in terms of methyl groups undergoing quantum rotational tunneling. (c) 2007 Elsevier Inc. All rights reserved.

Maan magneettikentän dipolimallin toimivuus inklinaatiojakauman perusteella

The magnetic field of the Earth is 99 % of the internal origin and generated in the outer liquid core by the dynamo principle. In the 19th century, Carl Friedrich Gauss proved that the field can be described by a sum of spherical harmonic terms. Presently, this theory is the basis of e.g. IGRF models (International Geomagnetic Reference Field), which are the most accurate description available for the geomagnetic field. In average, dipole forms 3/4 and non-dipolar terms 1/4 of the instantaneous field, but the temporal mean of the field is assumed to be a pure geocentric axial dipolar field. The validity of this GAD (Geocentric Axial Dipole) hypothesis has been estimated by using several methods. In this work, the testing rests on the frequency dependence of inclination with respect to latitude. Each combination of dipole (GAD), quadrupole (G2) and octupole (G3) produces a distinct inclination distribution. These theoretical distributions have been compared with those calculated from empirical observations from different continents, and last, from the entire globe. Only data from Precambrian rocks (over 542 million years old) has been used in this work. The basic assumption is that during the long-term course of drifting continents, the globe is sampled adequately. There were 2823 observations altogether in the paleomagnetic database of the University of Helsinki. The effect of the quality of observations, as well as the age and rocktype, has been tested. For comparison between theoretical and empirical distributions, chi-square testing has been applied. In addition, spatiotemporal binning has effectively been used to remove the errors caused by multiple observations. The modelling from igneous rock data tells that the average magnetic field of the Earth is best described by a combination of a geocentric dipole and a very weak octupole (less than 10 % of GAD). Filtering and binning gave distributions a more GAD-like appearance, but deviation from GAD increased as a function of the age of rocks. The distribution calculated from so called keypoles, the most reliable determinations, behaves almost like GAD, having a zero quadrupole and an octupole 1 % of GAD. In no earlier study, past-400-Ma rocks have given a result so close to GAD, but low inclinations have been prominent especially in the sedimentary data. Despite these results, a greater deal of high-quality data and a proof of the long-term randomness of the Earth's continental motions are needed to make sure the dipole model holds true.

Secondary flows induced by the rotation of a sphere or coaxial cones in micropolar fluids

The micropolar fluids like Newtonian and Non-Newtonian fluids cannot sustain a simple shearing motion, wherein only one component of velocity is present. They exhibit both primary and secondary motions when the boundaries are subject to slow rotations. The primary motion, as in Non-Newtonian fluids, characterized by the equation due to Rivlin-Ericksen, Oldroyd, Walters etc., resembles that of Newtonian fluid for slow steady rotation. We further notice that the micro-rotation becomes identically equal to the vorticity present in the fluid and the condition b) of "Wall vorticity" can alone be satisfied at the boundaries. As regards, the secondary motion, we notice that it can be determined by the above procedure for a special class of fluids, namely that for which j0(n2-n3)=4 n3/l2. Moreover for this class of fluids, the micro-rotation is identical with the vorticity of the fluid everywhere. Also the stream function for the secondary flow is identical with that for the Newtonian fluid with a suitable definition of the Reynolds number. In contrast with the Non-Newtonian fluids, characterized by the equation due to Rivlin-Ericksen, Oldroyd, Walters etc., this class of micropolar fluids does not show separation. This is in conformity with the statement of Condiff and Dahler (3) that in any steady flow, internal spin matches the vorticity everywhere provided that (i) spin boundary conditions are satisfied, (ii) body torques and non-conservative body forces are absent, and (iii) inertial and spin-inertial terms are either negligible or vanish identically.

Nonlinear aeroelasticity of rotating and flapping wings - a review

The interaction between large deflections, rotation effects and unsteady aerodynamics makes the dynamic analysis of rotating and flapping wing a nonlinear aeroelastic problem. This problem is governed by nonlinear periodic partial differential equations whose solution is needed to calculate the response and loads acting on vehicles using rotary or flapping wings for lift generation. We look at three important problems in this paper. The first problem shows the effect of nonlinear phenomenon coming from piezoelectric actuators used for helicopter vibration control. The second problem looks at the propagation on material uncertainty on the nonlinear response, vibration and aeroelastic stability of a composite helicopter rotor. The third problem considers the use of piezoelectric actuators for generating large motions in a dragonfly inspired flapping wing. These problems provide interesting insights into nonlinear aeroelasticity and show the likelihood of surprising phenomenon which needs to be considered during the design of rotary and flapping wing vehicle

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Vibrational force constant and electron relaxation in H2 and Li2

The force constants of H2 and Li2 are evaluated employing their extended Hartree-Fock wavefunctions by a polynomial fit of their force curves. It is suggested that, based on incomplete multiconfiguration Hartree-Fock wavefunctions, force constants calculated from the energy derivatives are numerically more accurate than those obtained from the derivatives of the Hellmann-Feynman forces. It is observed that electrons relax during the nuclear vibrations in such a fashion as to facilitate the nuclear motions.

Excited-state structures of molecules with nearby electronic states

Vibronic coupling among the nearby excited electronic states via the in-plane and the out-of-plane nuclear motions is examined in benzene, pyrazine, formaldehyde and thioformaldehyde. Results reveal that in benzene the structure distorts via the most active nuclear bending (planar) motion while in the other molecules the structures distort through an out-of-plane bending motion in their respective lowest excited states.

Inelastic Torsional Response of a Single-Story Framed Structure

In this paper, a single-story, bilinear-hysteretic structure, square in plan and supported on four columns, subjected to two horizontal ground motions is studied. The model is assumed to possess three degrees of freedom, viz., translational displacements along the two horizontal orthogonal directions and a rotation about the vertical axis. Interaction of the bending moments in the two perpendicular directions has been considered.

Temperature- and pressure-dependent study of Cl-35 NQR frequency and spin lattice relaxation time in 2,3-dichloroanisole

The temperature and pressure dependence of Cl-35 NQR frequency and spin lattice relaxation time (T-1) were investigated in 2,3-dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T-1 were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation f motion of the CH3 group. T-1 versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH3 group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules. Copyright (C) 2010 John Wiley & Sons, Ltd.

Critical age-dependent branching Markov processes and their scaling limits

This paper studies:(i)the long-time behaviour of the empirical distribution of age and normalized position of an age-dependent critical branching Markov process conditioned on non-extinction;and (ii) the super-process limit of a sequence of age-dependent critical branching Brownian motions.

Coupled ocean-atmosphere inter-decadal modes in the tropics

Homogencous upper air data for 50 years (1949-1998) from the National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis project, sea surface temperatures and sea level pressure are used to bring out the three dimensional structure of two dominant decadal/multi-decadal variations in the tropics. The global three dimensional modes represent generalized forms of inter-decadal modes studied earlier only with surface data. In the vertical, both modes show approximate first baroclinic structures over the tropics. The Walker circulation associated with the multidecadal mode has a wavenumber two structure in the zonal direction. It is shown that the magnitude of major ascending and descending motions associated with the multi-decadal Hadley and Walker circulations, are comparable to those associated with the dominant inter-annual mode. Implications of these large scale global circulations associated with the low frequency oscillations in modulating regional climate on a inter-annual time scale are discussed.

Total risk rating and stability analysis of embankment dams in the Kachchh Region, Gujarat, India

A method for total risk analysis of embankment dams under earthquake conditions is discussed and applied to the selected embankment dams, i.e., Chang, Tapar, Rudramata, and Kaswati located in the Kachchh region of Gujarat, India, to obtain the seismic hazard rating of the dam site and the risk rating of the structures. Based on the results of the total risk analysis of the dams, coupled non-linear dynamic numerical analyses of the dam sections are performed using acceleration time history record of the Bhuj (India) earthquake as well as five other major earthquakes recorded worldwide. The objective of doing so is to perform the numerical analysis of the dams for the range of amplitude, frequency content and time duration of input motions. The deformations calculated from the numerical analyses are also compared with other approaches available in literature, viz, Makdisi and Seed (1978) approach, Jansen's approach (1990), Swaisgood's method (1995), Bureau's method (1997). Singh et al. approach (2007), and Saygili and Rathje approach (2008) and the results are utilized to foresee the stability of dams in future earthquake scenario. (C) 2010 Elsevier B.V. All rights reserved.

Complexation of siRNA with Dendrimer: A Molecular Modeling Approach

This paper reports the structural behavior and thermodynamics of the complexation of siRNA with poly(amidoamine) (PAMAM) dendrimers of generation 3 (G3) and 4 (G4) through fully atomistic molecular dynamics (MD) simulations accompanied by free energy calculations and inherent structure determination. We have also done simulation with one siRNA and two dendrimers (2 x G3 or 2xG4) to get the microscopic picture of various binding modes. Our simulation results reveal the formation of stable siRNA-dendrimer complex over nanosecond time scale. With the increase in dendrimcr generation, the charge ratio increases and hence the binding energy between siRNA and dendrimer also increases in accordance with available experimental measurements. Calculated radial distribution functions of amines groups of various subgenerations in a given generation of dendrimer and phosphate in backbone of siRNA reveals that one dendrimer of generation 4 shows better binding with siRNA almost wrapping the dendrimer when compared to the binding with lower generation dendrimer like G3. In contrast, two dendrimers of generation 4 show binding without siRNA wrapping the den-rimer because of repulsion between two dendrimers. The counterion distribution around the complex and the water molecules in the hydration shell of siRNA give microscopic picture of the binding dynamics. We see a clear correlation between water. counterions motions and the complexation i.e. the water molecules and counterions which condensed around siRNA are moved away from the siRNA backbone when dendrimer start binding to the siRNA back hone. As siRNA wraps/bind to the dendrimer counterions originally condensed onto siRNA (Na-1) and dendrimer (Cl-) get released. We give a quantitative estimate of the entropy of counterions and show that there is gain in entropy due to counterions release during the complexation. Furthermore, the free energy of complexation of IG3 and IG4 at two different salt concentrations shows that increase in salt concentration leads to the weakening of the binding affinity of siRNA and dendrimer.

A theory on the migration of an extraneous electron across hydrogen bonds in polypeptides

The migrating electrons in biological systems normally are extraneous and taking this into account the electron delocalisation across the hydrogen bonds in proteins is re-examined. It is seen that an extraneous electron can travel rapidly via the low-lying virtual orbitals of the hydrogen-bonded π-electronic structure of peptide units in proteins. The frequency of electron transfer decreases slowly with an increase in the path length. However, the coupling of electron and protonic motions enhances this frequency. Transfer of electrons across the hydrogen bonds in accordance with the double-exchange mechanism does not appear to be possible. This theory offers a possibility for an extraneous electron to transfer within protein structures.

Miniature Compliant Grippers With Vision-Based Force Sensing

This paper is concerned with grasping biological cells in aqueous medium with miniature grippers that can also help estimate forces using vision-based displacement measurement and computation. We present the design, fabrication, and testing of three single-piece, compliant miniature grippers with parallel and angular jaw motions. Two grippers were designed using experience and intuition, while the third one was designed using topology optimization with implicit manufacturing constraints. These grippers were fabricated using different manufacturing techniques using spring steel and polydimethylsiloxane ( PDMS). The grippers also serve the purpose of a force sensor. Toward this, we present a vision-based force-sensing technique by solving Cauchy's problem in elasticity using an improved algorithm. We validated this technique at the macroscale, where there was an independent method to estimate the force. In this study, the gripper was used to hold a yeast ball and a zebrafish egg cell of less than 1 mm in diameter. The forces involved were estimated to be about 30 and 10 mN for the yeast ball and the zebrafish egg cell, respectively.