Monte Carlo simulations of molecular clusters in nucleation

A better understanding of the limiting step in a first order phase transition, the nucleation process, is of major importance to a variety of scientific fields ranging from atmospheric sciences to nanotechnology and even to cosmology. This is due to the fact that in most phase transitions the new phase is separated from the mother phase by a free energy barrier. This barrier is crossed in a process called nucleation. Nowadays it is considered that a significant fraction of all atmospheric particles is produced by vapor-to liquid nucleation. In atmospheric sciences, as well as in other scientific fields, the theoretical treatment of nucleation is mostly based on a theory known as the Classical Nucleation Theory. However, the Classical Nucleation Theory is known to have only a limited success in predicting the rate at which vapor-to-liquid nucleation takes place at given conditions. This thesis studies the unary homogeneous vapor-to-liquid nucleation from a statistical mechanics viewpoint. We apply Monte Carlo simulations of molecular clusters to calculate the free energy barrier separating the vapor and liquid phases and compare our results against the laboratory measurements and Classical Nucleation Theory predictions. According to our results, the work of adding a monomer to a cluster in equilibrium vapour is accurately described by the liquid drop model applied by the Classical Nucleation Theory, once the clusters are larger than some threshold size. The threshold cluster sizes contain only a few or some tens of molecules depending on the interaction potential and temperature. However, the error made in modeling the smallest of clusters as liquid drops results in an erroneous absolute value for the cluster work of formation throughout the size range, as predicted by the McGraw-Laaksonen scaling law. By calculating correction factors to Classical Nucleation Theory predictions for the nucleation barriers of argon and water, we show that the corrected predictions produce nucleation rates that are in good comparison with experiments. For the smallest clusters, the deviation between the simulation results and the liquid drop values are accurately modelled by the low order virial coefficients at modest temperatures and vapour densities, or in other words, in the validity range of the non-interacting cluster theory by Frenkel, Band and Bilj. Our results do not indicate a need for a size dependent replacement free energy correction. The results also indicate that Classical Nucleation Theory predicts the size of the critical cluster correctly. We also presents a new method for the calculation of the equilibrium vapour density, surface tension size dependence and planar surface tension directly from cluster simulations. We also show how the size dependence of the cluster surface tension in equimolar surface is a function of virial coefficients, a result confirmed by our cluster simulations.

Constraining scalar leptoquarks from the K and B sectors

Upper bounds at the weak scale are obtained for all lambda(ij)lambda(im) type product couplings of the scalar leptoquark model which may affect K-0 - (K) over bar (0), B-d - (B) over bar (d), and B-s - (B) over bar (s) mixing, as well as leptonic and semileptonic K and B decays. Constraints are obtained for both real and imaginary parts of the couplings. We also discuss the role of leptoquarks in explaining the anomalously large CP-violating phase in B-s - (B) over bar (s) mixing.

Generalised vortex motion of compressible fluid with and without magnetic field and suction

The laminar boundary layer over a stationary infinite disk induced by a rotating compressible fluid is considered. The free stream velocity has been taken as tangential and varies as a power of radius, i.e. v∞ ˜ r−n. The effect of the axial magnetic field and suction is also included in the analysis. An implicit finite difference scheme is employed to the governing similarity equations for numerical computations. Solutions are studied for various values of disk to fluid temperature ratio and for values of n between 1 and −1. In the absence of the magnetic field and suction, velocity profiles exhibit oscillations. It has been observed that for a hot disk in the presence of a magnetic field the boundary layer solutions decay algebraically instead of decaying exponentially. In the absence of the magnetic field and suction, the solution of the similarity equations exists only for a certain range of n.

Novel composite coded pattern for small angle measurement using imaging method -art.no.62891D

A novel approach for measurement of small rotation angles using imaging method is proposed and demonstrated. A plane mirror placed on a precision rotating table is used for imaging the newly designed composite coded pattern. The imaged patterns are captured with the help of a CCD camera. The angular rotation of the plane mirror is determined from a pair of the images of the pattern, captured once before and once after affecting the tilt of the mirror. Both simulation and experimental results suggest that the proposed approach not only retains the advantages of the original imaging method but also contributes significantly to the enhancement of its measuring range (+/- 4.13 degrees with accuracy of the order of 1 arcsec).

Thermal correlation functions of twisted quantum fields

We derive the thermal correlators for twisted quantum fields on noncommutative spacetime. We show that the thermal expectation value of the number operator is same as in commutative spacetime, but that higher correlators are sensitive to the noncommutativity parameters phi(mu nu).

Prediction of inplane damping from deterministic and stochastic models

This paper reviews computational reliability, computer algebra, stochastic stability and rotating frame turbulence (RFT) in the context of predicting the blade inplane mode stability, a mode which is at best weakly damped. Computational reliability can be built into routine Floquet analysis involving trim analysis and eigenanalysis, and a highly portable special purpose processor restricted to rotorcraft dynamics analysis is found to be more economical than a multipurpose processor. While the RFT effects are dominant in turbulence modeling, the finding that turbulence stabilizes the inplane mode is based on the assumption that turbulence is white noise.

Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH3CONH2), urea (NH2CONH2) and ammonium nitrate (NH4NO3). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step. 2-electron pathways of O-2 to H2O2 and further reduction of H2O2 to H2O. The first 2-electron reduction of O-2 to H2O2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and ROE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BOO) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide. (C) 2010 Elsevier Ltd. All rights reserved.

Helicopter blade flapping with and without small angle assumption in the presence of dynamic stall

The flapping equation for a rotating rigid helicopter blade is typically derived by considering (1)small flap angle, (2) small induced angle of attack and (3) linear aerodynamics. However, the use of nonlinear aerodynamics such as dynamic stall can make the assumptions of small angles suspect as shown in this paper. A general equation describing helicopter blade flap dynamics for large flap angle and large induced inflow angle of attack is derived. A semi-empirical dynamic stall aerodynamics model (ONERA model) is used. Numerical simulations are performed by solving the nonlinear flapping ordinary differential equation for steady state conditions and the validity of the small angle approximations are examined. It is shown that the small flapping assumption, and to a lesser extent, the small induced angle ofattack assumption, can lead to inaccurate predictions of the blade flap response in certain flight conditions for some rotors when nonlinear aerodynamics is considered. (C) 2010 Elsevier Inc. All rights reserved.

Apsidal motion in 4U 0115+63 and orbital parameters of 2S 1417-624 and V0332+53

Be/X-ray binary pulsars have wide eccentric orbits and hence the angle of periastron of the orbit is very well defined in these sources. The presence of an X-ray pulsar allows for accurate measurements of orbital elements. A Be star usually is a rapidly rotating star and hence will deviate from spherical geometry. The tidal interaction between the neutron star and the Be star will add to the distortion of the Be star and alter its mass distribution. Thus a measurable rate of apsidal motion is expected from these systems. In this paper, we present the first conclusive detection of apsidal motion of the binary 4U 0115+63. We also present new and accurate orbital parameters of the Be/X-ray binaries V0332+53 and 2S 1417-624.

The stress in a slowly sheared granular column

We report measurements of the wall stress in a granular material sheared in a cylindrical Couette cell, as a function of the distance from the free surface. Our results shows that when the material is static, all components of the stress saturate to constant values within a short distance from the free surface, in conformity with earlier experiments and theoretical predictions. When the material is sheared by rotating the inner cylinder at a constant rate, the stresses are remarkably altered. The radial normal stress does not saturate, and increases even more rapidly with depth than the linear hydrostatic pressure profile. The axial shear stress changes sign on shearing, and its magnitude increases with depth. These results are discussed in the context of the predictions of the classical and Cosserat plasticity theories.

Crystallization and preliminary X-ray crystallographic analysis of a galactose-specific lectin from Dolichos lablab

The galactose-specific lectin from the seeds of Dolichos lablab has been crystallized using the hanging-drop vapour-diffusion technique. The crystals belong to space group P1, with unit-cell parameters a = 73.99, b = 84.13, c = 93.15 angstrom, alpha = 89.92, beta = 76.01, gamma = 76.99 degrees. X-ray diffraction data to a resolution of 3.0 angstrom have been collected under cryoconditions ( 100 K) using a MAR imaging-plate detector system mounted on a rotating-anode X-ray generator. Molecular-replacement calculations carried out using the available structures of legume lectins as search models revealed that the galactose-specific lectin from D. lablab forms a tetramer similar to soybean agglutinin; two such tetramers are present in the asymmetric unit.

A singularity-free cosmological model in ECSK theory

In the framework of the ECSK [Einstein-Cartan-Sciama-Kibble] theory of cosmology, a scalar field nonminimally coupled to the gravitational field is considered. For a Robertson-Walker open universe (k=0) in the radiation era, the field equations admit a singularity-free solution for the scale factor. In theory, the torsion is generated through nonminimal coupling of a scalar field to the gravitation field. The nonsingular nature of the cosmological model automatically solves the flatness problem. Further absence of event horizon and particle horizon explains the high degree of isotropy, especially of 2.7-K background radiation.

Parametrized tests of post-Newtonian theory using Advanced LIGO and Einstein Telescope

General relativity has very specific predictions for the gravitational waveforms from inspiralling compact binaries obtained using the post-Newtonian (PN) approximation. We investigate the extent to which the measurement of the PN coefficients, possible with the second generation gravitational-wave detectors such as the Advanced Laser Interferometer Gravitational-Wave Observatory (LIGO) and the third generation gravitational-wave detectors such as the Einstein Telescope (ET), could be used to test post-Newtonian theory and to put bounds on a subclass of parametrized-post-Einstein theories which differ from general relativity in a parametrized sense. We demonstrate this possibility by employing the best inspiralling waveform model for nonspinning compact binaries which is 3.5PN accurate in phase and 3PN in amplitude. Within the class of theories considered, Advanced LIGO can test the theory at 1.5PN and thus the leading tail term. Future observations of stellar mass black hole binaries by ET can test the consistency between the various PN coefficients in the gravitational-wave phasing over the mass range of 11-44M(circle dot). The choice of the lower frequency cutoff is important for testing post-Newtonian theory using the ET. The bias in the test arising from the assumption of nonspinning binaries is indicated.

Micropillar Array Based Microchips for Electrospray Ionization Mass Spectrometry, Microreactors, and Liquid Chromatographic Separation

This dissertation deals with the design, fabrication, and applications of microscale electrospray ionization chips for mass spectrometry. The microchip consists of microchannel, which leads to a sharp electrospray tip. Microchannel contain micropillars that facilitate a powerful capillary action in the channels. The capillary action delivers the liquid sample to the electrospray tip, which sprays the liquid sample to gas phase ions that can be analyzed with mass spectrometry. The microchip uses a high voltage, which can be utilized as a valve between the microchip and mass spectrometry. The microchips can be used in various applications, such as for analyses of drugs, proteins, peptides, or metabolites. The microchip works without pumps for liquid transfer, is usable for rapid analyses, and is sensitive. The characteristics of performance of the single microchips are studied and a rotating multitip version of the microchips are designed and fabricated. It is possible to use the microchip also as a microreactor and reaction products can be detected online with mass spectrometry. This property can be utilized for protein identification for example. Proteins can be digested enzymatically on-chip and reaction products, which are in this case peptides, can be detected with mass spectrometry. Because reactions occur faster in a microscale due to shorter diffusion lengths, the amount of protein can be very low, which is a benefit of the method. The microchip is well suited to surface activated reactions because of a high surface-to-volume ratio due to a dense micropillar array. For example, titanium dioxide nanolayer on the micropillar array combined with UV radiation produces photocatalytic reactions which can be used for mimicking drug metabolism biotransformation reactions. Rapid mimicking with the microchip eases the detection of possibly toxic compounds in preclinical research and therefore could speed up the research of new drugs. A micropillar array chip can also be utilized in the fabrication of liquid chromatographic columns. Precisely ordered micropillar arrays offer a very homogenous column, where separation of compounds has been demonstrated by using both laser induced fluorescence and mass spectrometry. Because of small dimensions on the microchip, the integrated microchip based liquid chromatography electrospray microchip is especially well suited to low sample concentrations. Overall, this work demonstrates that the designed and fabricated silicon/glass three dimensionally sharp electrospray tip is unique and facilitates stable ion spray for mass spectrometry.

Measurement of the ttbar production cross section with an in situ calibration of b-jet identification efficiency

A measurement of the top-quark pair-production cross section in ppbar collisions at sqrt{s}=1.96 TeV using data corresponding to an integrated luminosity of 1.12/fb collected with the Collider Detector at Fermilab is presented. Decays of top-quark pairs into the final states e nu + jets and mu nu + jets are selected, and the cross section and the b-jet identification efficiency are determined using a new measurement technique which requires that the measured cross sections with exactly one and multiple identified b-quarks from the top-quark decays agree. Assuming a top-quark mass of 175 GeV/c^2, a cross section of 8.5+/-0.6(stat.)+/-0.7(syst.) pb is measured.