Dissipative dynamics of a harmonic oscillator: A nonperturbative approach

Starting from a microscopic theory, we derive a master equation for a harmonic oscillator coupled to a bath of noninteracting oscillators. We follow a nonperturbative approach, proposed earlier by us for the free Brownian particle. The diffusion constants are calculated analytically and the positivity of the master equation is shown to hold above a critical temperature. We compare the long time behavior of the average kinetic and potential energies with known thermodynamic results. In the limit of vanishing oscillator frequency of the system, we recover the results of the free Brownian particle.

ESR study of copper diethyldithiophosphate

ESR investigations are reported in single crystals of copper diethyldithiophosphate, magnetically diluted with the corresponding diamagnetic nickel complex. The spectrum at normal gain shows hyperfine components from 63Cu, 65Cu, and 31P nuclei. At much higher gain, hyperfine interaction from 33S nuclei in the ligand is detected. The spin Hamiltonian parameters relating to copper show tetragonal symmetry. The measured parameters are g|| = 2.085, g[perpendicular]=2.025, A63Cu = 149.6 × 10−4 cm−1, A65Cu = 160.8 × 10−4 cm−1, BCu = 32.5 × 10−4 cm−1 and QCu [infinity] 5.5 × 10−4cm−1. The 31P interaction is isotropic with a coupling constant AP = 9.6 × 10−4 cm−1. Angular variation of the 33S lines shows two different hyperfine tensors indicating the presence of two chemically inequivalent Cu[Single Bond]S bonds. The experimentally determined hyperfine constants are A ₁^s=34.9×10−4 cm−1, B ₁^s=26.1×10−4 cm−1, A ₂^s=60.4×10−4 cm−1, B₂^s=55.5×10−4 cm−1. The hyperfine parameters show that the hybridization of the ligand orbitals is very sensitive to the symmetry around the ligand. The g values and Cu hyperfine parameters are not much affected by the distortions occurring in the ligand. The energies of the d-d transitions are determined by optical absorption measurements on Cu diethyldithiophosphate in solution. Using the spin Hamiltonian parameters together with optical absorption results, the MO parameters for the complex are calculated. It is found that in addition to the sigma bond, the pi bonds are also strongly covalent. ©1973 The American Institute of Physics.

Diffusion of localized optical excitations and trap emission in ruby

Using the critical percolation conductance method the energy-dependent diffusion coefficient associated with thermally assisted transfer of the R1 line excitation between single Cr3+ ions with strain-induced randomness has been calculated in the 4A2 to E(2E) transition energies. For localized states sufficiently far away from the mobility edge the energy transfer is dominated by dipolar interactions, while very close to the mobility edge it is determined by short-range exchange interactions. Using the above energy-dependent diffusion coefficient a macroscopic diffusion equation is solved for the rate of light emission by Cr3+ ion-pair traps to which single-ion excitations are transferred. The dipolar mechanism leads to good agreement with recent measurements of the pair emission rate by Koo et al. (Phys. Rev. Lett., vol.35, p.1669 (1975)) right up to the mobility edge.

Studies on the reduction of hematite by carbon

Single pellet experiments have been carried out in a nitrogen atmosphere to study the reduction of hematite by graphite in the temperature range 925 to 1060°C. The effect of variables such as c/Fe2O3 molar ratio, pellet size, and so forth, has been investigated. Gas analysis data show a continuous decrease in CO2/CO ratio during reduction, the values being far away from Fe/FeO equilibrium for wustite reduction by CO. The activation energies associated with different degrees of reduction appear to be widely different suggesting a possible changeover in reaction mechanism during the progress of reduction. X-ray diffraction studies confirm the stepwise nature of hematite reduction.

The hydrogen bond: a molecular beam microwave spectroscopist's view with a universal appeal

In this manuscript, we propose a criterion for a weakly bound complex formed in a supersonic beam to be characterized as a `hydrogen bonded complex'. For a `hydrogen bonded complex', the zero point energy along any large amplitude vibrational coordinate that destroys the orientational preference for the hydrogen bond should be significantly below the barrier along that coordinate so that there is at least one bound level. These are vibrational modes that do not lead to the breakdown of the complex as a whole. If the zero point level is higher than the barrier, the `hydrogen bond' would not be able to stabilize the orientation which favors it and it is no longer sensible to characterize a complex as hydrogen bonded. Four complexes, Ar-2-H2O, Ar-2-H2S, C2H4-H2O and C2H4-H2S, were chosen for investigations. Zero point energies and barriers for large amplitude motions were calculated at a reasonable level of calculation, MP2(full)/aug-cc-pVTZ, for all these complexes. Atoms in molecules (AIM) theoretical analyses of these complexes were carried out as well. All these complexes would be considered hydrogen bonded according to the AIM theoretical criteria suggested by Koch and Popelier for C-H center dot center dot center dot O hydrogen bonds (U. Koch and P. L. A. Popelier, J. Phys. Chem., 1995, 99, 9747), which has been widely and, at times, incorrectly used for all types of contacts involving H. It is shown that, according to the criterion proposed here, the Ar-2-H2O/H2S complexes are not hydrogen bonded even at zero kelvin and C2H4-H2O/H2S complexes are. This analysis can naturally be extended to all temperatures. It can explain the recent experimental observations on crystal structures of H2S at various conditions and the crossed beam scattering studies on rare gases with H2O and H2S.

Effect of mechanical cycling on the stress-strain response of a martensitic Nitinol shape memory alloy

An experimental investigation into the ambient temperature, load-controlled tension�tension fatigue behavior of a martensitic Nitinol shape memory alloy (SMA) was conducted. Fatigue life for several stress levels spanning the critical stress for detwinning was determined and compared with that obtained on an alloy similar in composition but in the austenitic state at room temperature. Results show that the fatigue life of the pseudo-plastic alloy is superior to superelastic shape memory alloy. The stress�strain hysteretic response, monitored throughout the fatigue loading, reveals progressive strain accumulation with the cyclic loading. In addition, the area of hysteresis and recoverable and frictional energies were found to decrease with increasing number of fatigue cycles. Post-mortem characterization of the fatigued specimens through calorimetry and fractography was conducted in order to get further insight into the fatigue micromechanisms. These results are discussed in terms of reversible and irreversible microstructural changes that take place during cyclic loading. Aspects associated with self-heating of martensitic alloy undergoing high frequency stress cycling are discussed.

Theoretical calculations of base-base interactions in nucleic acids: II Stacking interactions in polynucleotides

Base-base interactions were computed for single- and double- stranded polynucleotides, for all possible base sequences. In each case, both right and left stacking arrangements are energetically possible. The preference of one over the other depends upon the base-sequence and the orientation of the bases with respect to helix-axis. Inverted stacking arrangement is also energetically possible for both single- and double-stranded polynucleotides. Finally, interaction energies of a regular duplex and the alternative structures3 were compared. It was found that the type II model3 is energetically more favourable than the rest.

Which One Is Preferred: Myers-Saito Cyclization of Ene-Yne-Allene or Garratt-Braverman Cyclization of Conjugated Bisallenic Sulfone? A Theoretical and Experimental Study

A competitive scenario between Myers-Saito (MS) and Garraff-Braverman (GB) cyclization has been created in a molecule. High-level computations indicate a preference for GB over MS cyclization. The activation energies for the rate-determining steps of the GB and MS cyclizations were found to be the same (24.4 kcal/mol) at the B3LYP/6-31G* level of theory; thus, from the kinetic point of view, both reactions are feasible. However, the main biradical intermediate GB2 of the GB reaction is 6.2 kcal/mol lower in energy than the biradical MS2, which is the main intermediate of MS reaction, so GB cyclization is thermodynamically favored over MS cyclization. To verify the prediction by computational techniques, bisenediynyl sulfones 1-4 and bisenediynyl sulfoxide 17 were synthesized. Under basic conditions, these molecules isomerized to a system possessing both the ene-yne-allene and the bisallenic sulfone. The isolation of only one product, identified as the corresponding naphthalene- or benzene-fused sulfone 8-11, indicated the occurrence of GB cyclization as the sole reaction pathway. No product corresponding to the MS cyclization pathway could be isolated. Though the theoretical prediction showed a preference for the GB pathway over the MS pathway, the exclusive preference for GB over MS cyclization is very striking. Further analysis showed that the intramolecular self-quenching nature of the GB pathway may play an important role in the complete preference for this reaction. Apart from the mechanistic studies, these sulfones showed DNA cleavage activity that had an inverse relation with the reactivity order. Our findings are important for the design of artificial DNA-cleaving agents.

A comparative molecular dynamics study of diffusion of n-decane and 3-methyl pentane in Y zeolite

Molecular dynamics simulations are reported on the structure and dynamics of n-decane and 3-methylpentane in zeolite NaY. We have calculated several properties such as the center of mass-center of mass rdf, the end-end distance distribution, bond angle distribution and dihedral angle distribution. We have also analysed trajectory to obtain diffusivity and velocity autocorrelation function (VACF). Surprisingly, the diffusivity of 3-methylpentane which is having larger cross-section perpendicular to the long molecular axis is higher than n-decane at 300 K. Activation energies have been obtained from simulations performed at 200 K, 300 K, 350 K, 400 K and 450 K in the NVE ensemble. These results can be understood in terms of the previously known levitation effect. Arrhenious plot has higher value of slope for n-decane (5 center dot 9 kJ/mol) than 3-methylpentane (3 center dot 7 kJ/mol) in agreement with the prediction of levitation effect.

Design, Development, Synthesis, and Docking Analysis of 2-substituted Triclosan Analogs as Inhibitors for Plasmodium falciparum Enoyl-ACP Reductase

A structure-based approach has been adopted to develop 2'substituted analogs of triclosan. The Cl at position 2' in ring B of triclosan was chemically substituted with other functional groups like NH2, NO2 and their inhibitory potencies against PfENR were determined. The binding energies of the 2' substituted analogs of triclosan for enoyl-acyl carrier protein reductase (ENR) of Plasmodium falciparum were determined using Autodock. Based on the autodock results, we synthesized the potential compounds. The IC50 and inhibition constant (K-i) of 2' substituted analogs of triclosan were determined against purified PfENR. Among them, two compounds,2-(2'-Amino-4'-chloro-phenoxy)-5-chloro-phenol (compound 4) and 5-chloro-2-(4'-chloro-2'-nitro-phenoxy)-phenol) (compound 5) exhibited good potencies. Compound 4 followed uncompetitive inhibition kinetics with crotonoyl CoA and competitive with NADH. It was shown to have an IC50 of 110 nM; inhibition constant was 104 nM with the substrate and 61 nM with the cofactor. IC50 Of compound 5 was determined to be 229 nM. Compounds 4 and 5 showed significant inhibition of the parasite growth in P. falciparum culture. (C) 2009 IUBMB IUBMB Life, 61(11):1083-1091, 2009.

Search for chaos in neutron star systems: Is Cyg X-3 a black hole?

The accretion disk around a compact object is a nonlinear general relativistic system involving magnetohydrodynamics. Naturally, the question arises whether such a system is chaotic (deterministic) or stochastic (random) which might be related to the associated transport properties whose origin is still not confirmed. Earlier, the black hole system GRS 1915+105 was shown to be low-dimensional chaos in certain temporal classes. However, so far such nonlinear phenomena have not been studied fairly well for neutron stars which are unique for their magnetosphere and kHz quasi-periodic oscillation (QPO). On the other hand, it was argued that the QPO is a result of nonlinear magnetohydrodynamic effects in accretion disks. If a neutron star exhibits chaotic signature, then what is the chaotic/correlation dimension? We analyze RXTE/PCA data of neutron stars Sco X-1 and Cyg X-2, along with the black hole Cyg X-1 and the unknown source Cyg X-3, and show that while Sco X-1 and Cyg X-2 are low dimensional chaotic systems, Cyg X-1 and Cyg X-3 are stochastic sources. Based on our analysis, we argue that Cyg X-3 may be a black hole.

Crystallization kinetics of SrBi2B2O7 glasses by non-isothermal methods

Transparent glasses of SrBi2B2O7 (SBBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC). The glass transition (T (g)) and the crystallization parameters [crystallization activation energy (E (cr)) and Avrami exponent (n)] were evaluated under non-isothermal conditions using DSC. There was a close agreement between the activation energies for the crystallization process determined by Augis and Bennet and Kissinger methods. The variation of local activation energy [E (c)(x)] that was determined by Ozawa method, decreased with the fraction of crystallization (x). The Avrami exponent (n(x)) increased with the increase in fraction of crystallization (x) suggesting that there was a change over in the crystallization process from the surface to the bulk.

W physics at the ILC with polarized beams as a probe of the Littlest Higgs model

We study the possibility of using W pair production and leptonic decay of one of the W's at the ILC with polarized beams as a probe of the Littlest Higgs Model. We consider cross-sections, polarization fractions of the W's, leptonic decay energy and angular distributions, and left-right polarization asymmetry as probes of the model. With parameter values allowed by present experimental constraints detectable effects on these observables at typical ILC energies of 500 GeV and 800 GeV will be present. Beam polarization is further found to enhance the sensitivity.

Stuffed fullerenelike boron carbide nanoclusters

Viable stuffed fullerenelike boron carbide nanoclusters, C50B34, C48B36-2, and their isomers based on an icosahedral B-84 fragment of elemental beta-rhombohedral boron have been investigated using density functional theory calculations. The structure and the stability of these clusters are rationalized using the polyhedral skeletal electron counting and ring-cap orbital overlap compatibility rules. The curvature of the fullerene was found to play a vital role in achieving the most stable isomer C50B34(3B). The large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, three dimensional aromaticity, and electron detachment energies support their high stability. Further, the IR and Raman active modes were recognized.

A model of the polarization position-angle swings in BL Lacertae objects

The polarization position-angle swings that have been measured in a number of BL Lacertae objects and highly variable quasars are interpreted in terms of shock waves which illuminate (by enhanced synchrotron radiation) successive transverse cross sections of a magnetized, relativistic jet. The jet is assumed to have a nonaxisymmetric magnetic field configuration of the type discussed in the companion paper on the equilibria of force-free jets. For a jet that is viewed at a small angle to the axis, the passage of a shock will give rise to an apparent rotation of the polarization position angle whose amplitude can be substantially larger than 180 deg. The effects of freely propagating shocks are compared with those of bow shocks which form in front of dense obstacles in the jet, and specific applications to 0727 - 115 and BL Lacertae are considered. In the case of 0727 - 115, it is pointed out that the nonuniformity of the swing rate and the apparent oscillations of the degree of polarization could be a consequence of relativistic aberration.