Remarkably large captodative stabilisation in radical ions

Palladium complex-catalyzed carbonylation of arylsulfonyl chlorides in the presence of metal alkoxides M(OR)n (M=B, Al, and Ti) gives the corresponding esters along with diaryl disulfides. With metal carboxylates M(OCOR)n (M=Na, K, Ca, Mg, and Zn), the free acids are also obtained

Constructing a Community : Myths and Realities of the Open Development Model

The open development model of software production has been characterized as the future model of knowledge production and distributed work. Open development model refers to publicly available source code ensured by an open source license, and the extensive and varied distributed participation of volunteers enabled by the Internet. Contemporary spokesmen of open source communities and academics view open source development as a new form of volunteer work activity characterized by hacker ethic and bazaar governance . The development of the Linux operating system is perhaps the best know example of such an open source project. It started as an effort by a user-developer and grew quickly into a large project with hundreds of user-developer as contributors. However, in hybrids , in which firms participate in open source projects oriented towards end-users, it seems that most users do not write code. The OpenOffice.org project, initiated by Sun Microsystems, in this study represents such a project. In addition, the Finnish public sector ICT decision-making concerning open source use is studied. The purpose is to explore the assumptions, theories and myths related to the open development model by analysing the discursive construction of the OpenOffice.org community: its developers, users and management. The qualitative study aims at shedding light on the dynamics and challenges of community construction and maintenance, and related power relations in hybrid open source, by asking two main research questions: How is the structure and membership constellation of the community, specifically the relation between developers and users linguistically constructed in hybrid open development? What characterizes Internet-mediated virtual communities and how can they be defined? How do they differ from hierarchical forms of knowledge production on one hand and from traditional volunteer communities on the other? The study utilizes sociological, psychological and anthropological concepts of community for understanding the connection between the real and the imaginary in so-called virtual open source communities. Intermediary methodological and analytical concepts are borrowed from discourse and rhetorical theories. A discursive-rhetorical approach is offered as a methodological toolkit for studying texts and writing in Internet communities. The empirical chapters approach the problem of community and its membership from four complementary points of views. The data comprises mailing list discussion, personal interviews, web page writings, email exchanges, field notes and other historical documents. The four viewpoints are: 1) the community as conceived by volunteers 2) the individual contributor s attachment to the project 3) public sector organizations as users of open source 4) the community as articulated by the community manager. I arrive at four conclusions concerning my empirical studies (1-4) and two general conclusions (5-6). 1) Sun Microsystems and OpenOffice.org Groupware volunteers failed in developing necessary and sufficient open code and open dialogue to ensure collaboration thus splitting the Groupware community into volunteers we and the firm them . 2) Instead of separating intrinsic and extrinsic motivations, I find that volunteers unique patterns of motivations are tied to changing objects and personal histories prior and during participation in the OpenOffice.org Lingucomponent project. Rather than seeing volunteers as a unified community, they can be better understood as independent entrepreneurs in search of a collaborative community . The boundaries between work and hobby are blurred and shifting, thus questioning the usefulness of the concept of volunteer . 3) The public sector ICT discourse portrays a dilemma and tension between the freedom to choose, use and develop one s desktop in the spirit of open source on one hand and the striving for better desktop control and maintenance by IT staff and user advocates, on the other. The link between the global OpenOffice.org community and the local end-user practices are weak and mediated by the problematic IT staff-(end)user relationship. 4) Authoring community can be seen as a new hybrid open source community-type of managerial practice. The ambiguous concept of community is a powerful strategic tool for orienting towards multiple real and imaginary audiences as evidenced in the global membership rhetoric. 5) The changing and contradictory discourses of this study show a change in the conceptual system and developer-user relationship of the open development model. This change is characterized as a movement from hacker ethic and bazaar governance to more professionally and strategically regulated community. 6) Community is simultaneously real and imagined, and can be characterized as a runaway community . Discursive-action can be seen as a specific type of online open source engagement. Hierarchies and structures are created through discursive acts. Key words: Open Source Software, open development model, community, motivation, discourse, rhetoric, developer, user, end-user

Relaxation system based sub-grid scale modelling for large eddy simulation of Burgers' equation

An implicit sub-grid scale model for large eddy simulation is presented by utilising the concept of a relaxation system for one dimensional Burgers' equation in a novel way. The Burgers' equation is solved for three different unsteady flow situations by varying the ratio of relaxation parameter (epsilon) to time step. The coarse mesh results obtained with a relaxation scheme are compared with the filtered DNS solution of the same problem on a fine mesh using a fourth-order CWENO discretisation in space and third-order TVD Runge-Kutta discretisation in time. The numerical solutions obtained through the relaxation system have the same order of accuracy in space and time and they closely match with the filtered DNS solutions.

Essays on labour demand and wage formation

The first essay in this thesis is on gender wage differentials among manufacturing sector white-collar workers. The wage differential is decomposed into firm, job (within-firm) and individ-ual-level components. Job-level gender segregation explains over half of the gap, while firm-level segregation is not important. After controlling for firm, job and individual characteristics, the remaining unexplained wage cap to the advantage of men is six per cent of men s mean wage. In the second essay, I study how the business cycle and gender affect the distribution of the earnings losses of displaced workers. The negative effect of displacement is large, persistent and strongest in the lowest earnings deciles. The effect is larger in a recession than in a recov-ery period, and in all periods women s earnings drop more than men s earnings. The third essay shows that the transition from steady employment to disability pension de-pends on the stringency of medical screening and the degree of experience-rating of pension costs applied to the employer. The fact that firms have to bear part of the cost of employees disability pension costs lowers both the incidence of long sick leave periods and the probabil-ity that sick leave ends in a disability pension. The fourth and fifth essays are studies on the employment, wage and profit effects of a re-gional payroll tax cut experiment conducted in northern and eastern Finland. The results show no statistically significant effect on any of the response variables.

Meridional propagation of large-scale monsoon convective zones

Observational studies indicate that the convective activity of the monsoon systems undergo intraseasonal variations with multi-week time scales. The zone of maximum monsoon convection exhibits substantial transient behavior with successive propagating from the North Indian Ocean to the heated continent. Over South Asia the zone achieves its maximum intensity. These propagations may extend over 3000 km in latitude and perhaps twice the distance in longitude and remain as coherent entities for periods greater than 2-3 weeks. Attempts to explain this phenomena using simple ocean-atmosphere models of the monsoon system had concluded that the interactive ground hydrology so modifies the total heating of the atmosphere that a steady state solution is not possible, thus promoting lateral propagation. That is, the ground hydrology forces the total heating of the atmosphere and the vertical velocity to be slightly out of phase, causing a migration of the convection towards the region of maximum heating. Whereas the lateral scale of the variations produced by the Webster (1983) model were essentially correct, they occurred at twice the frequency of the observed events and were formed near the coastal margin, rather than over the ocean. Webster's (1983) model used to pose the theories was deficient in a number of aspects. Particularly, both the ground moisture content and the thermal inertia of the model were severely underestimated. At the same time, the sea surface temperatures produced by the model between the equator and the model's land-sea boundary were far too cool. Both the atmosphere and the ocean model were modified to include a better hydrological cycle and ocean structure. The convective events produced by the modified model possessed the observed frequency and were generated well south of the coastline. The improved simulation of monsoon variability allowed the hydrological cycle feedback to be generalized. It was found that monsoon variability was constrained to lie within the bounds of a positive gradient of a convective intensity potential (I). The function depends primarily on the surface temperature, the availability of moisture and the stability of the lower atmosphere which varies very slowly on the time scale of months. The oscillations of the monsoon perturb the mean convective intensity potential causing local enhancements of the gradient. These perturbations are caused by the hydrological feedbacks, discussed above, or by the modification of the air-sea fluxes caused by variations of the low level wind during convective events. The final result is the slow northward propagation of convection within an even slower convective regime. The ECMWF analyses show very similar behavior of the convective intensity potential. Although it is considered premature to use the model to conduct simulations of the African monsoon system, the ECMWF analysis indicates similar behavior in the convective intensity potential suggesting, at least, that the same processes control the low frequency structure of the African monsoon. The implications of the hypotheses on numerical weather prediction of monsoon phenomenon are discussed.

Dependence of the large-scale vortex instability on latitude, stratification and domain size

In an earlier study, we reported on the excitation of large-scale vortices in Cartesian hydrodynamical convection models subject to rapid enough rotation. In that study, the conditions for the onset of the instability were investigated in terms of the Reynolds (Re) and Coriolis (Co) numbers in models located at the stellar North pole. In this study, we extend our investigation to varying domain sizes, increasing stratification, and place the box at different latitudes. The effect of the increasing box size is to increase the sizes of the generated structures, so that the principal vortex always fills roughly half of the computational domain. The instability becomes stronger in the sense that the temperature anomaly and change in the radial velocity are observed to be enhanced. The model with the smallest box size is found to be stable against the instability, suggesting that a sufficient scale separation between the convective eddies and the scale of the domain is required for the instability to work. The instability can be seen upto the colatitude of 30 degrees, above which value the flow becomes dominated by other types of mean flows. The instability can also be seen in a model with larger stratification. Unlike the weakly stratified cases, the temperature anomaly caused by the vortex structures is seen to depend on depth.

Elliptic flow of thermal photons in heavy-ion collisions at Relativistic Heavy Ion Collider and Large Hadron Collider

We calculate the thermal photon transverse momentum spectra and elliptic flow in $\sqrt{s_{NN}} = 200$ GeV Au+Au collisions at RHIC and in $\sqrt{s_{NN}} = 2.76$ TeV Pb+Pb collisions at the LHC, using an ideal-hydrodynamical framework which is constrained by the measured hadron spectra at RHIC and LHC. The sensitivity of the results to the QCD-matter equation of state and to the photon emission rates is studied, and the photon $v_2$ is discussed in the light of the photonic $p_T$ spectrum measured by the PHENIX Collaboration. In particular, we make a prediction for the thermal photon $p_T$ spectra and elliptic flow for the current LHC Pb+Pb collisions.

Texture evolution and operative mechanisms during large-strain deformation of nanocrystalline nickel

The large-strain deformation of nanocrystalline nickel was investigated at room temperature and cryogenic (liquid N-2) temperature. Deformation mechanisms ranging from grain boundary sliding to slip, operate due to a wide distribution of grain sizes. These mechanisms leave their finger print in the deformation texture evolution during rolling of nanocrystalline nickel. The occurrence and severance of different mechanisms is understood by a thorough characterization of the deformed samples using X-ray diffraction, X-ray texture measurements, electron back-scattered diffraction and transmission electron microscopy. Crystal plasticity-based viscoplastic self-consistent simulations were used to further substantiate the experimental observations. Thus, a comprehensive understanding of deformation behavior of nanocrystalline nickel, which is characterized by simultaneous operation of dislocation-dominated and grain boundary-mediated mechanisms, has been developed.

Guessing Revisited: A Large Deviations Approach

The problem of guessing a random string is revisited. A close relation between guessing and compression is first established. Then it is shown that if the sequence of distributions of the information spectrum satisfies the large deviation property with a certain rate function, then the limiting guessing exponent exists and is a scalar multiple of the Legendre-Fenchel dual of the rate function. Other sufficient conditions related to certain continuity properties of the information spectrum are briefly discussed. This approach highlights the importance of the information spectrum in determining the limiting guessing exponent. All known prior results are then re-derived as example applications of our unifying approach.

Large negative magnetoresistance and metal-insulator transition observed in MnO/C composite coatings grown on ceramic alumina by metalorganic chemical vapor deposition

MnO/C composite coatings were grown by the metalorganic chemical vapor deposition process on ceramic alumina in argon ambient. Characterization by various techniques confirms that these coatings are homogeneous composites comprising nanometer-sized MnO particles embedded in a matrix of nanometer-sized graphite. Components of the MnO/C composite coating crystalline disordered, but are electrically quite conductive. Resistance vs. temperature measurements show that coating resistance increases exponentially from a few hundred ohms at room temperature to a few megaohms at 30 K. Logarithmic plots of reduced activation energy vs. temperature show that the coating material undergoes a metal-insulator transition. The reduced activation energy exponent for the film under zero magnetic field was 2.1, which is unusually high, implying that conduction is suppressed at much faster rate than the Mott or the Efros-Shklovskii hopping mechanism. Magnetoconductance us. magnetic field plots obtained at various temperatures show a high magnetoconductance (similar to 28.8%) at 100 K, which is unusually large for a disordered system, wherein magnetoresistance is attributed typically to weak localization. A plausible explanation for the unusual behavior observed in the carbonaceous disordered composite material is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Large-Signal Model for Independent DG MOSFET

In this paper, we show the limitations of the traditional charge linearization techniques for modeling terminal charges of the independent double-gate metal-oxide-semiconductor field-effect transistors. Based on our recent computationally efficient Poisson solution for independent double gate transistors, we propose a new charge linearization technique to model the terminal charges and transcapacitances. We report two different types of quasistatic large-signal models for the long-channel device. In the first type, the terminal charges are expressed as closed-form functions of the source- and drain-end inversion charge densities and found to be accurate when the potential distribution at source end of the channel is hyperbolic in nature. The second type, which is found to be accurate in all regimes of operations, is based on the quadratic spline collocation technique and requires the input voltage equation to be solved two more times, apart from the source and drain ends.

Symmetry Properties of the Large-Deviation Function of the Velocity of a Self-Propelled Polar Particle

A geometrically polar granular rod confined in 2D geometry, subjected to a sinusoidal vertical oscillation, undergoes noisy self-propulsion in a direction determined by its polarity. When surrounded by a medium of crystalline spherical beads, it displays substantial negative fluctuations in its velocity. We find that the large-deviation function (LDF) for the normalized velocity is strongly non-Gaussian with a kink at zero velocity, and that the antisymmetric part of the LDF is linear, resembling the fluctuation relation known for entropy production, even when the velocity distribution is clearly non-Gaussian. We extract an analogue of the phase-space contraction rate and find that it compares well with an independent estimate based on the persistence of forward and reverse velocities.

High-Rate Space-Time Coded Large MIMO Systems: Low-Complexity Detection and Performance

Large MIMO systems with tens of antennas in each communication terminal using full-rate non-orthogonal space-time block codes (STBC) from Cyclic Division Algebras (CDA) can achieve the benefits of both transmit diversity as well as high spectral efficiencies. Maximum-likelihood (ML) or near-ML decoding of these large-sized STBCs at low complexities, however, has been a challenge. In this paper, we establish that near-ML decoding of these large STBCs is possible at practically affordable low complexities. We show that the likelihood ascent search (LAS) detector, reported earlier by us for V-BLAST, is able to achieve near-ML uncoded BER performance in decoding a 32x32 STBC from CDA, which employs 32 transmit antennas and sends 32(2) = 1024 complex data symbols in 32 time slots in one STBC matrix (i.e., 32 data symbols sent per channel use). In terms of coded BER, with a 16x16 STBC, rate-3/4 turbo code and 4-QAM (i.e., 24 bps/Hz), the LAS detector performs close to within just about 4 dB from the theoretical MIMO capacity. Our results further show that, with LAS detection, information lossless (ILL) STBCs perform almost as good as full-diversity ILL (FD-ILL) STBCs. Such low-complexity detectors can potentially enable implementation of high spectral efficiency large MIMO systems that could be considered in wireless standards.

Layered Tabu Search Algorithm for Large-MIMO Detection and a Lower Bound on ML Performance

In this paper, we are concerned with low-complexity detection in large multiple-input multiple-output (MIMO) systems with tens of transmit/receive antennas. Our new contributions in this paper are two-fold. First, we propose a low-complexity algorithm for large-MIMO detection based on a layered low-complexity local neighborhood search. Second, we obtain a lower bound on the maximum-likelihood (ML) bit error performance using the local neighborhood search. The advantages of the proposed ML lower bound are i) it is easily obtained for MIMO systems with large number of antennas because of the inherent low complexity of the search algorithm, ii) it is tight at moderate-to-high SNRs, and iii) it can be tightened at low SNRs by increasing the number of symbols in the neighborhood definition. Interestingly, the proposed detection algorithm based on the layered local search achieves bit error performances which are quite close to this lower bound for large number of antennas and higher-order QAM. For e. g., in a 32 x 32 V-BLAST MIMO system, the proposed detection algorithm performs close to within 1.7 dB of the proposed ML lower bound at 10(-3) BER for 16-QAM (128 bps/Hz), and close to within 4.5 dB of the bound for 64-QAM (192 bps/Hz).

Crossover dynamics at large metastability in gas-liquid nucleation

We have developed an alternate description of dynamics of nucleation in terms of an extended set of order parameters. The order parameters consist of an ordered set of kth largest clusters, ordered such that k = 1 is the largest cluster in the system, k = 2 is the second largest cluster, and so on. We have derived an analytic expression for the free energy for the kth largest cluster, which is in excellent agreement with the simulated results. At large supersaturation, the free energy barrier for the growth of the kth largest cluster disappears and the nucleation becomes barrierless. The major success of this extended theoretical formalism is that it can clearly explain the observed change in mechanism at large metastability P. Bhimalapuram et al., Phys. Rev. Lett. 98, 206104 (2007)] and the associated dynamical crossover. The classical nucleation theory cannot explain this crossover. The crossover from activated to barrierless nucleation is found to occur at a supersaturation where multiple clusters cross the critical size. We attribute the crossover as the onset of the kinetic spinodal. We have derived an expression for the rate of nucleation in the barrierless regime by modeling growth as diffusion on the free energy surface of the largest cluster. The model reproduces the slower increase in the rate of growth as a function of supersaturation, as observed in experiments.