The role of intramolecular barriers on the glass transition of polymers: computer simulations versus mode coupling theory

We present computer simulations of a simple bead-spring model for polymer melts with intramolecular barriers. By systematically tuning the strength of the barriers, we investigate their role on the glass transition. Dynamic observables are analyzed within the framework of the mode coupling theory (MCT). Critical nonergodicity parameters, critical temperatures, and dynamic exponents are obtained from consistent fits of simulation data to MCT asymptotic laws. The so-obtained MCT λ-exponent increases from standard values for fully flexible chains to values close to the upper limit for stiff chains. In analogy with systems exhibiting higher-order MCT transitions, we suggest that the observed large λ-values arise form the interplay between two distinct mechanisms for dynamic arrest: general packing effects and polymer-specific intramolecular barriers. We compare simulation results with numerical solutions of the MCT equations for polymer systems, within the polymer reference interaction site model (PRISM) for static correlations. We verify that the approximations introduced by the PRISM are fulfilled by simulations, with the same quality for all the range of investigated barrier strength. The numerical solutions reproduce the qualitative trends of simulations for the dependence of the nonergodicity parameters and critical temperatures on the barrier strength. In particular, the increase in the barrier strength at fixed density increases the localization length and the critical temperature. However the qualitative agreement between theory and simulation breaks in the limit of stiff chains. We discuss the possible origin of this feature.

Model studies on the synthesis of the natural meroterpenoid cordiaquinone A

Two main strategies for the synthesis of the natural meroterpenoid cordiaquinone A (1) - isolated of the roots of Cordia corymbosa G. Don (Boraginaceae) - were tested on model compounds. Whereas all attempts of alkylation of epsilon-caprolactone (10) were unsuccessful, the coupling of epoxycitronellol (17) with an appropriate organocuprate proceeded in the expected direction.

A simple model for circadian timing by mammals

Circadian timing is structured in such a way as to receive information from the external and internal environments, and its function is the timing organization of the physiological and behavioral processes in a circadian pattern. In mammals, the circadian timing system consists of a group of structures, which includes the suprachiasmatic nucleus (SCN), the intergeniculate leaflet and the pineal gland. Neuron groups working as a biological pacemaker are found in the SCN, forming a biological master clock. We present here a simple model for the circadian timing system of mammals, which is able to reproduce two fundamental characteristics of biological rhythms: the endogenous generation of pulses and synchronization with the light-dark cycle. In this model, the biological pacemaker of the SCN was modeled as a set of 1000 homogeneously distributed coupled oscillators with long-range coupling forming a spherical lattice. The characteristics of the oscillator set were defined taking into account the Kuramoto's oscillator dynamics, but we used a new method for estimating the equilibrium order parameter. Simultaneous activities of the excitatory and inhibitory synapses on the elements of the circadian timing circuit at each instant were modeled by specific equations for synaptic events. All simulation programs were written in Fortran 77, compiled and run on PC DOS computers. Our model exhibited responses in agreement with physiological patterns. The values of output frequency of the oscillator system (maximal value of 3.9 Hz) were of the order of magnitude of the firing frequencies recorded in suprachiasmatic neurons of rodents in vivo and in vitro (from 1.8 to 5.4 Hz).

Calculation of the magnetic field penetration depth for high-Tc cuprate superconductors based on the Interlayer Pair Tunneling model /

In this work, the magnetic field penetration depth for high-Tc cuprate superconductors is calculated using a recent Interlayer Pair Tunneling (ILPT) model proposed by Chakravarty, Sudb0, Anderson, and Strong [1] to explain high temperature superconductivity. This model involves a "hopping" of Cooper pairs between layers of the unit cell which acts to amplify the pairing mechanism within the planes themselves. Recent work has shown that this model can account reasonably well for the isotope effect and the dependence of Tc on nonmagnetic in-plane impurities [2] , as well as the Knight shift curves [3] and the presence of a magnetic peak in the neutron scattering intensity [4]. In the latter case, Yin et al. emphasize that the pair tunneling must be the dominant pairing mechanism in the high-Tc cuprates in order to capture the features found in experiments. The goal of this work is to determine whether or not the ILPT model can account for the experimental observations of the magnetic field penetration depth in YBa2Cu307_a7. Calculations are performed in the weak and strong coupling limits, and the efi"ects of both small and large strengths of interlayer pair tunneling are investigated. Furthermore, as a follow up to the penetration depth calculations, both the neutron scattering intensity and the Knight shift are calculated within the ILPT formalism. The aim is to determine if the ILPT model can yield results consistent with experiments performed for these properties. The results for all three thermodynamic properties considered are not consistent with the notion that the interlayer pair tunneling must be the dominate pairing mechanism in these high-Tc cuprate superconductors. Instead, it is found that reasonable agreement with experiments is obtained for small strengths of pair tunneling, and that large pair tunneling yields results which do not resemble those of the experiments.

Chaotic, memory, and cooling rate effects in spin glasses: Evaluation of the Edwards-Anderson model

We investigate chaotic, memory, and cooling rate effects in the three-dimensional Edwards-Anderson model by doing thermoremanent (TRM) and ac susceptibility numerical experiments and making a detailed comparison with laboratory experiments on spin glasses. In contrast to the experiments, the Edwards-Anderson model does not show any trace of reinitialization processes in temperature change experiments (TRM or ac). A detailed comparison with ac relaxation experiments in the presence of dc magnetic field or coupling distribution perturbations reveals that the absence of chaotic effects in the Edwards-Anderson model is a consequence of the presence of strong cooling rate effects. We discuss possible solutions to this discrepancy, in particular the smallness of the time scales reached in numerical experiments, but we also question the validity of the Edwards-Anderson model to reproduce the experimental results.

Ab initio theoretical comparative study of magnetic coupling in KNiF3 and K2NiF4s

The origin of magnetic coupling in KNiF3 and K2 NiF4 is studied by means of an ab initio cluster model approach. By a detailed study of the mapping between eigenstates of the exact nonrelativistic and spin model Hamiltonians it is possible to obtain the magnetic coupling constant J and to compare ab initio cluster-model values with those resulting from ab initio periodic Hartree-Fock calculations. This comparison shows that J is strongly determined by two-body interactions; this is a surprising and unexpected result. The importance of the ligands surrounding the basic metal-ligand-metal interacting unit is reexamined by using two different partitions and the constrained space orbital variation method of analysis. This decomposition enables us to show that this effect is basically environmental. Finally, dynamical electronic correlation effects have found to be critical in determining the final value of the magnetic coupling constant.

Local character of magnetic coupling in ionic solids

Magnetic interactions in ionic solids are studied using parameter-free methods designed to provide accurate energy differences associated with quantum states defining the Heisenberg constant J. For a series of ionic solids including KNiF3, K2NiF4, KCuF3, K2CuF4, and high- Tc parent compound La2CuO4, the J experimental value is quantitatively reproduced. This result has fundamental implications because J values have been calculated from a finite cluster model whereas experiments refer to infinite solids. The present study permits us to firmly establish that in these wide-gap insulators, J is determined from strongly local electronic interactions involving two magnetic centers only thus providing an ab initio support to commonly used model Hamiltonians.

Effective t-J model Hamiltonian parameters of monolayered cuprate superconductors from ab initio electronic structure calculations

The magnetic coupling constant of selected cuprate superconductor parent compounds has been determined by means of embedded cluster model and periodic calculations carried out at the same level of theory. The agreement between both approaches validates the cluster model. This model is subsequently employed in state-of-the-art configuration interaction calculations aimed to obtain accurate values of the magnetic coupling constant and hopping integral for a series of superconducting cuprates. Likewise, a systematic study of the performance of different ab initio explicitly correlated wave function methods and of several density functional approaches is presented. The accurate determination of the parameters of the t-J Hamiltonian has several consequences. First, it suggests that the appearance of high-Tc superconductivity in existing monolayered cuprates occurs with J/t in the 0.20¿0.35 regime. Second, J/t=0.20 is predicted to be the threshold for the existence of superconductivity and, third, a simple and accurate relationship between the critical temperatures at optimum doping and these parameters is found. However, this quantitative electronic structure versus Tc relationship is only found when both J and t are obtained at the most accurate level of theory.

Model Calculations and Implementation of Filters and Hybrid Green VCSELs based on Optical Thin Film Stacks

This work introduced the novel conception of complex coupled hybrid VCSELs for the first time. Alternating organic and inorganic layers in the lasers provide periodic variation of refractive index and optical gain, which enable single mode operation and low threshold of the VCSELs. Model calculations revealed great reduction of the lasing threshold with factors over 30, in comparison with the existing micro-cavity lasers. Tunable green VCSEL has been also designed, implemented and analyzed taking advantage of the broad photoluminescence spectra of the organics. Free standing optical thin films without compressive stress are technologically implemented. Multiple membrane stacks with air gap in between have been fabricated for the implementation of complex coupled VCSEL structures. Complex coupled hybrid VCSEL is a very promising approach to fill the gaps in the green spectral range of the semiconductor lasers.

Solar influences on dynamical coupling between the stratosphere and troposphere

We use a simplified atmospheric general circulation model (AGCM) to investigate the response of the lower atmosphere to thermal perturbations in the lower stratosphere. The results show that generic heating of the lower stratosphere tends to weaken the sub-tropical jets and the tropospheric mean meridional circulations. The positions of the jets, and the extent of the Hadley cells, respond to the distribution of the stratospheric heating, with low latitude heating displacing them poleward, and uniform heating displacing them equatorward. The patterns of response to the low latitude heating are similar to those found to be associated with solar variability in previous observational data analysis, and to the effects of varying solar UV radiation in sophisticated AGCMs. In order to investigate the chain of causality involved in converting the stratospheric thermal forcing to a tropospheric climate signal we conduct an experiment which uses an ensemble of model spin-ups to analyse the time development of the response to an applied stratospheric perturbation. We find that the initial effect of the change in static stability at the tropopause is to reduce the eddy momentum flux convergence in this region. This is followed by a vertical transfer of the momentum forcing anomaly by an anomalous mean circulation to the surface, where it is partly balanced by surface stress anomalies. The unbalanced part drives the evolution of the vertically integrated zonal flow. We conclude that solar heating of the stratosphere may produce changes in the circulation of the troposphere even without any direct forcing below the tropopause. We suggest that the impact of the stratospheric changes on wave propagation is key to the mechanisms involved.

The effect of doubled CO2 and model basic state biases on the monsoon-ENSO system. II: Changing ENSO regimes

Integrations of a fully-coupled climate model with and without flux adjustments in the equatorial oceans are performed under 2×CO2 conditions to explore in more detail the impact of increased greenhouse gas forcing on the monsoon-ENSO system. When flux adjustments are used to correct some systematic model biases, ENSO behaviour in the modelled future climate features distinct irregular and periodic (biennial) regimes. Comparison with the observed record yields some consistency with ENSO modes primarily based on air-sea interaction and those dependent on basinwide ocean wave dynamics. Simple theory is also used to draw analogies between the regimes and irregular (stochastically forced) and self-excited oscillations respectively. Periodic behaviour is also found in the Asian-Australian monsoon system, part of an overall biennial tendency of the model under these conditions related to strong monsoon forcing and increased coupling between the Indian and Pacific Oceans. The tropospheric biennial oscillation (TBO) thus serves as a useful descriptor for the coupled monsoon-ENSO system in this case. The presence of obvious regime changes in the monsoon-ENSO system on interdecadal timescales, when using flux adjustments, suggests there may be greater uncertainty in projections of future climate, although further modelling studies are required to confirm the realism and cause of such changes.

Geostatistical Tools for Validation of Satellite and NWP Model Rainfall

An eclectic morphostratigraphic model for the sedimentary response to Holocene sea-level rise in northwest Europe

The improved empirical understanding of silt facies in Holocene coastal sequences provided by such as diatom, foraminifera, ostracode and testate amoebae analysis, combined with insights from quantitative stratigraphic and hydraulic simulations, has led to an inclusive, integrated model for the palaeogeomorphology, stratigraphy, lithofacies and biofacies of northwest European Holocene coastal lowlands in relation to sea-level behaviour. The model covers two general circumstances and is empirically supported by a range of field studies in the Holocene deposits of a number of British estuaries, particularly, the Severn. Where deposition was continuous over periods of centuries to millennia, and sea level fluctuated about a rising trend, the succession consists of repeated cycles of silt and peat lithofacies and biofacies in which series of transgressive overlaps (submergence sequences) alternate with series of regressive overlaps (emergence sequences) in association with the waxing and waning of tidal creek networks. Environmental and sea-level change are closely coupled, and equilibrium and secular pattern is of the kind represented ideally by a closed limit cycle. In the second circumstance, characteristic of unstable wetland shores and generally affecting smaller areas, coastal erosion ensures that episodes of deposition in the high intertidal zone last no more than a few centuries. The typical response is a series of regressive overlaps (emergence sequence) in erosively based high mudflat and salt-marsh silts that record, commonly as annual banding, exceptionally high deposition rates and a state of strong disequilibrium. Environmental change, including creek development, and sea-level movement are uncoupled. Only if deposition proceeds for a sufficiently long period, so that marshes mature, are equilibrium and close coupling regained. (C) 2002 Elsevier Science B.V. All rights reserved.

Coupled simulations of the Indian monsoon intraseasonal oscillation using a fine-resolution mixed-layer ocean model

The intraseasonal variability (ISV) of the Indian summer monsoon is dominated by a 30–50 day oscillation between “active” and “break” events of enhanced and reduced rainfall over the subcontinent, respectively. These organized convective events form in the equatorial Indian Ocean and propagate north to India. Atmosphere–ocean coupled processes are thought to play a key role the intensity and propagation of these events. A high-resolution, coupled atmosphere–mixed-layer-oceanmodel is assembled: HadKPP. HadKPP comprises the Hadley Centre Atmospheric Model (HadAM3) and the K Profile Parameterization (KPP) mixed-layer ocean model. Following studies that upper-ocean vertical resolution and sub-diurnal coupling frequencies improve the simulation of ISV in SSTs, KPP is run at 1 m vertical resolution near the surface; the atmosphere and ocean are coupled every three hours. HadKPP accurately simulates the 30–50 day ISV in rainfall and SSTs over India and the Bay of Bengal, respectively, but suffers from low ISV on the equator. This is due to the HadAM3 convection scheme producing limited ISV in surface fluxes. HadKPP demonstrates little of the observed northward propagation of intraseasonal events, producing instead a standing oscillation. The lack of equatorial ISV in convection in HadAM3 constrains the ability of KPP to produce equatorial SST anomalies, which further weakens the ISV of convection. It is concluded that while atmosphere–ocean interactions are undoubtedly essential to an accurate simulation of ISV, they are not a panacea for model deficiencies. In regions where the atmospheric forcing is adequate, such as the Bay of Bengal, KPP produces SST anomalies that are comparable to the Tropical Rainfall Measuring Mission Microwave Imager (TMI) SST analyses in both their magnitude and their timing with respect to rainfall anomalies over India. HadKPP also displays a much-improved phase relationship between rainfall and SSTs over a HadAM3 ensemble forced by observed SSTs, when both are compared to observations. Coupling to mixed-layer models such as KPP has the potential to improve operational predictions of ISV, particularly when the persistence time of SST anomalies is shorter than the forecast lead time.

El Nino-mean state-seasonal cycle interactions in a multi-model ensemble

The modelled El Nino-mean state-seasonal cycle interactions in 23 coupled ocean-atmosphere GCMs, including the recent IPCC AR4 models, are assessed and compared to observations and theory. The models show a clear improvement over previous generations in simulating the tropical Pacific climatology. Systematic biases still include too strong mean and seasonal cycle of trade winds. El Nino amplitude is shown to be an inverse function of the mean trade winds in agreement with the observed shift of 1976 and with theoretical studies. El Nino amplitude is further shown to be an inverse function of the relative strength of the seasonal cycle. When most of the energy is within the seasonal cycle, little is left for inter-annual signals and vice versa. An interannual coupling strength (ICS) is defined and its relation with the modelled El Nino frequency is compared to that predicted by theoretical models. An assessment of the modelled El Nino in term of SST mode (S-mode) or thermocline mode (T-mode) shows that most models are locked into a S-mode and that only a few models exhibit a hybrid mode, like in observations. It is concluded that several basic El Nino-mean state-seasonal cycle relationships proposed by either theory or analysis of observations seem to be reproduced by CGCMs. This is especially true for the amplitude of El Nino and is less clear for its frequency. Most of these relationships, first established for the pre-industrial control simulations, hold for the double and quadruple CO2 stabilized scenarios. The models that exhibit the largest El Nino amplitude change in these greenhouse gas (GHG) increase scenarios are those that exhibit a mode change towards a T-mode (either from S-mode to hybrid or hybrid to T-mode). This follows the observed 1976 climate shift in the tropical Pacific, and supports the-still debated-finding of studies that associated this shift to increased GHGs. In many respects, these models are also among those that best simulate the tropical Pacific climatology (ECHAM5/MPI-OM, GFDL-CM2.0, GFDL-CM2.1, MRI-CGM2.3.2, UKMO-HadCM3). Results from this large subset of models suggest the likelihood of increased El Nino amplitude in a warmer climate, though there is considerable spread of El Nino behaviour among the models and the changes in the subsurface thermocline properties that may be important for El Nino change could not be assessed. There are no clear indications of an El Nino frequency change with increased GHG.