Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold
International Nuclear Information System (INIS)
Leitner, David M.; Wolynes, Peter G.
2006-01-01
A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states
The rate coefficients of unimolecular reactions in the systems with power-law distributions
Yin, Cangtao; Guo, Ran; Du, Jiulin
2014-08-01
The rate coefficient formulae of unimolecular reactions are generalized to the systems with the power-law distributions based on nonextensive statistics, and the power-law rate coefficients are derived in the high and low pressure limits, respectively. The numerical analyses are made of the rate coefficients as functions of the ν-parameter, the threshold energy, the temperature and the number of degrees of freedom. We show that the new rate coefficients depend strongly on the ν-parameter different from one (thus from a Boltzmann-Gibbs distribution). Two unimolecular reactions, CH3CO→CH3+CO and CH3NC→CH3CN, are taken as application examples to calculate their power-law rate coefficients, which obtained with the ν-parameters slightly different from one can be exactly in agreement with all the experimental studies on these two reactions in the given temperature ranges.
Unimolecular decomposition reactions at low-pressure: A comparison of competitive methods
Adams, G. F.
1980-01-01
The lack of a simple rate coefficient expression to describe the pressure and temperature dependence hampers chemical modeling of flame systems. Recently developed simplified models to describe unimolecular processes include the calculation of rate constants for thermal unimolecular reactions and recombinations at the low pressure limit, at the high pressure limit and in the intermediate fall-off region. Comparison between two different applications of Troe's simplified model and a comparison between the simplified model and the classic RRKM theory are described.
International Nuclear Information System (INIS)
Maillard, S.; Skorek, R.; Maugis, P.; Dumont, M.
2015-01-01
This chapter presents the basic principles of cluster dynamics as a particular case of mesoscopic rate theory models developed to investigate fuel behaviour under irradiation such as in UO 2 . It is shown that as this method simulates the evolution of the concentration of every type of point or aggregated defect in a grain of material. It produces rich information that sheds light on the mechanisms involved in microstructure evolution and gas behaviour that are not accessible through conventional models but yet can provide for improvements in those models. Cluster dynamics parameters are mainly the energetic values governing the basic evolution mechanisms of the material (diffusion, trapping and thermal resolution). In this sense, the model has a general applicability to very different operational situations (irradiation, ion-beam implantation, annealing) provided that they rely on the same basic mechanisms, without requiring additional data fitting, as is required for more empirical conventional models. This technique, when applied to krypton implanted and annealed samples, yields a precise interpretation of the release curves and helps assess migration mechanisms and the krypton diffusion coefficient, for which data is very difficult to obtain due to the low solubility of the gas. (authors)
J.G.M. van Marrewijk (Charles)
2005-01-01
textabstractThis four-chapter overview of basic exchange rate theories discusses (i) the elasticity and absorption approach, (ii) the (long-run) implications of the monetary approach, (iii) the short-run effects of monetary and fiscal policy under various economic conditions, and (iv) the transition
Zhou, Chong-Wen; Li, Ze-Rong; Liu, Cun-Xi; Li, Xiang-Yuan
2008-12-01
Enols have been found to be important intermediates in the combustion flames of hydrocarbon [C. A. Taatjes et al., Science 308, 1887 (2005)]. The removal mechanism of enols in combustion flame has not been established yet. In this work, the potential energy surface for the unimolecular decomposition of syn-propen-2-ol and H+CH2COHCH2 recombination reactions have been first investigated by CCSD(T) method. The barrier heights, reaction energies, and geometrical parameters of the reactants, products, intermediates, and transition states have been investigated theoretically. The results show that the formation of CH3CO+CH3 via the CH3COCH3 intermediate is dominant for the unimolecular decomposition of syn-propen-2-ol and its branching ratio is over 99% in the whole temperature range from 700 to 3000 K, and its rate constant can be expressed as an analytical form in the range of T =700-3000 K at atmospheric pressure. This can be attributed to the lower energy barrier of this channel compared to the other channels. The association reaction of H with CH2COHCH2 is shown to be a little more complicated than the unimolecular decomposition of syn-propen-2-ol. The channel leading to CH3CO+CH3 takes a key role in the whole temperature range at atmospheric pressure. However at the higher pressure of 100 atm, the recombination by direct formation of syn-propen-2-ol through H addition is important at T 1400 K, the recombination channel leading to CH3CO+CH3 turns out to be significant.
Falivene, Laura
2018-04-24
Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.
High-temperature unimolecular decomposition of ethyl propionate
Giri, Binod; Alabbad, Mohammed; Farooq, Aamir
2016-01-01
This work reports rate coefficients of the thermal unimolecular decomposition reaction of ethyl propionate (EP) behind reflected shock waves over the temperature range of 976–1300 K and pressures of 825–1875 Torr. The reaction progress was monitored
Green, Amy M; Barber, Victoria P; Fang, Yi; Klippenstein, Stephen J; Lester, Marsha I
2017-11-21
Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3 CHOO. IR excitation of selectively deuterated syn -CD 3 CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn -CD 3 CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn -CH 3 CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50.
Decontamination by Water-Soluble Unimolecular Metallopolymers
National Research Council Canada - National Science Library
Newkcome, George
1998-01-01
...., diaminopyridine, bipyridine, or piperazine); the development of branched monomers and branched quaternary ammonium capping reagents, which offered a novel entree to supramolecular chemistry within unimolecular systems...
Yang, Mino
2007-06-07
Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.
Predicted thermochemistry and unimolecular kinetics of nitrous sulfide
DEFF Research Database (Denmark)
Marshall, Paul; Gao, Yide; Glarborg, Peter
2011-01-01
The geometry of N2S was obtained at the CCSD(T)/aug-cc-pV(T + d)Z level of theory and energies with coupled-cluster single double triple (CCSD(T)) and basis sets up to aug-cc-pV(6 + d)Z. After correction for anharmonic zero-point energy, core-valence correlation, correlation up to CCSDT...... crossing point between singlet and triplet potential energy curves is found at r(N-N) approximate to 1.105 angstrom and r(N-S) approximate to 2.232 angstrom, with an energy 72 kJ mol (1) above N-2 + S(P-3). Application of Troe's unimolecular formalism yields the low-pressure-limiting rate constant......(Q) and relativistic effects, D-0 for the N-S bond is estimated as 71.9 kJ mol (1), and the corresponding thermochemistry for N2S is Delta H-f(0)degrees = 205.4 kJ mol(-1) and Delta H-f(298)degrees = 202.6 kJ mol(-1) with an uncertainty of +/- 2.5 kJ mol(-1). Using CCSD(T)/aug-cc-pV(T + d) theory the minimum energy...
Tunneling and reflection in unimolecular reaction kinetic energy release distributions
Hansen, K.
2018-02-01
The kinetic energy release distributions in unimolecular reactions is calculated with detailed balance theory, taking into account the tunneling and the reflection coefficient in three different types of transition states; (i) a saddle point corresponding to a standard RRKM-type theory, (ii) an attachment Langevin cross section, and (iii) an absorbing sphere potential at short range, without long range interactions. Corrections are significant in the one dimensional saddle point states. Very light and lightly bound absorbing systems will show measurable effects in decays from the absorbing sphere, whereas the Langevin cross section is essentially unchanged.
On the high-temperature unimolecular decomposition of ethyl levulinate
Alabbad, Mohammed; Giri, Binod; Szőri, Milá n; Farooq, Aamir
2016-01-01
The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.
On the high-temperature unimolecular decomposition of ethyl levulinate
Alabbad, Mohammed
2016-09-20
The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.
Unimolecular reaction dynamics of free radicals
International Nuclear Information System (INIS)
Terry A. Miller
2006-01-01
Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy
Strickland, Ken
2013-04-01
The Rate Change Big Bang Theory redefines the birth of the universe with a dramatic shift in energy direction and a new vision of the first moments. With rate change graph technology (RCGT) we can look back 13.7 billion years and experience every step of the big bang through geometrical intersection technology. The analysis of the Big Bang includes a visualization of the first objects, their properties, the astounding event that created space and time as well as a solution to the mystery of anti-matter.
A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate
Alabbad, Mohammed
2017-07-08
Thermal unimolecular decomposition of diethyl carbonate (DEC) was investigated in a shock tube by measuring ethylene concentration with a CO2 gas laser over 900 - 1200 K and 1.2 – 2.8 bar. Rate coefficients were extracted using a simple kinetic scheme comprising of thermal decomposition of DEC as initial step followed by rapid thermal decomposition of the intermediate ethyl-hydrogen-carbonate. Our results were further analysed using ab initio and master equation calculations to obtain pressure- and temperature- dependence of rate coefficients. Similar to alkyl esters, unimolecular decomposition of DEC is found to undergo six-center retro-ene elimination of ethylene in a concerted manner.
A High Temperature Kinetic Study for the Thermal Unimolecular Decomposition of Diethyl Carbonate
Alabbad, Mohammed; Giri, Binod; Szőri, Milan; Viskolcz, Bé la; Farooq, Aamir
2017-01-01
Thermal unimolecular decomposition of diethyl carbonate (DEC) was investigated in a shock tube by measuring ethylene concentration with a CO2 gas laser over 900 - 1200 K and 1.2 – 2.8 bar. Rate coefficients were extracted using a simple kinetic scheme comprising of thermal decomposition of DEC as initial step followed by rapid thermal decomposition of the intermediate ethyl-hydrogen-carbonate. Our results were further analysed using ab initio and master equation calculations to obtain pressure- and temperature- dependence of rate coefficients. Similar to alkyl esters, unimolecular decomposition of DEC is found to undergo six-center retro-ene elimination of ethylene in a concerted manner.
Unimolecular and collisionally induced ion reactions
International Nuclear Information System (INIS)
Beynon, J.H.; Boyd, R.K.
1978-01-01
The subject is reviewed under the following headings: introduction (mass spectroscopy and the study of fragmentation reactions of gaseous positive ions); techniques and methods (ion sources, detection systems, analysis of ions, data reduction); collision-induced reactions of ions and unimolecular fragmentations of metastable ions; applications (ion structure, energetic measurements, analytical applications, other applications). 305 references. (U.K.)
Energy Technology Data Exchange (ETDEWEB)
Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States); Klippenstein, Stephen J. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)
2016-07-28
The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.
Dressing effect in multiphoton unimolecular dissociation
Energy Technology Data Exchange (ETDEWEB)
Gonzalez-Diaz, P.F.; Garcia-Fernandez, P.
1986-03-01
On the basis of a quantum-statistical model recently discussed, we deal in this paper with the perturbations induced by the intense field of a CO/sub 2/ laser on the levels of the vibrational pattern of a molecule undergoing multiphoton unimolecular dissociation. This perturbational correction is investigated by using a displacement operator technique and the results are interpreted according to the statistical model.
High-temperature unimolecular decomposition of ethyl propionate
Giri, Binod
2016-10-09
This work reports rate coefficients of the thermal unimolecular decomposition reaction of ethyl propionate (EP) behind reflected shock waves over the temperature range of 976–1300 K and pressures of 825–1875 Torr. The reaction progress was monitored by detecting CH near 10.532 μm using CO gas laser absorption. In addition, G3//MP2/aug-cc-pVDZ and master equation calculations were performed to assess the pressure- and temperature-dependence of the reaction. Our calculations revealed that CH elimination occurs via a six-centered retro-ene transition state. Our measured rate data are close to the high-pressure limit and showed no discernable temperature fall off.
Paul, Amit K; Hase, William L
2016-01-28
A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations.
Theory of nanolaser devices: Rate equation analysis versus microscopic theory
DEFF Research Database (Denmark)
Lorke, Michael; Skovgård, Troels Suhr; Gregersen, Niels
2013-01-01
A rate equation theory for quantum-dot-based nanolaser devices is developed. We show that these rate equations are capable of reproducing results of a microscopic semiconductor theory, making them an appropriate starting point for complex device simulations of nanolasers. The input...
Microcanonical rates, gap times, and phase space dividing surfaces
Ezra, Gregory S.; Waalkens, Holger; Wiggins, Stephen
2009-01-01
The general approach to classical unimolecular reaction rates due to Thiele is revisited in light of recent advances in the phase space formulation of transition state theory for multidimensional systems. Key concepts, such as the phase space dividing surface separating reactants from products, the
Information theory and rate distortion theory for communications and compression
Gibson, Jerry
2013-01-01
This book is very specifically targeted to problems in communications and compression by providing the fundamental principles and results in information theory and rate distortion theory for these applications and presenting methods that have proved and will prove useful in analyzing and designing real systems. The chapters contain treatments of entropy, mutual information, lossless source coding, channel capacity, and rate distortion theory; however, it is the selection, ordering, and presentation of the topics within these broad categories that is unique to this concise book. While the cover
Competing reaction channels in IR-laser-induced unimolecular reactions
International Nuclear Information System (INIS)
Berman, M.R.
1981-01-01
The competing reaction channels in the unimolecular decomposition of two molecules, formaldehyde and tetralin were studied. A TEA CO 2 laser was used as the excitation source in all experiments. The dissociation of D 2 CO was studied by infrared multiphoton dissociation (MPD) and the small-molecule nature of formaldehyde with regard to MPD was explored. The effect of collisions in MPD were probed by the pressure dependence of the MPD yield and ir fluorescence from multiphoton excited D 2 CO. MPD yield shows a near cubic dependence in pure D 2 CO which is reduced to a 1.7 power dependence when 15 torr of NO is added. The peak amplitude of 5 μm ir fluorescence from D 2 CO is proportional to the square of the D 2 CO pressure in pure D 2 CO or in the presence of 50 torr of Ar. Results are explained in terms of bottlenecks to excitation at the v = 1 level which are overcome by a combination of vibrational energy transfer and rotational relaxation. The radical/molecule branching ratio in D 2 CO MPD was 0.10 +- 0.02 at a fluence of 125 J/cm 2 at 946.0 cm -1 . The barrier height to molecular dissociation was calculated to be 3.6 +- 2.0 kcal/mole below the radical threshold or 85.0 +- 3.0 kcal/mole above the ground state of D 2 CO. In H 2 CO, this corresponds to 2.5 +- 2.0 kcal/mole below the radical threshold or 83.8 +- 3.0 kcal/mole above the ground state. Comparison with uv data indicate that RRKM theory is an acceptable description of formaldehyde dissociation in the 5 to 10 torr pressure range. The unimolecular decomposition of tetralin was studied by MPD and SiF 4 - sensitized pyrolysis. Both techniques induce decomposition without the interference of catalytic surfaces. Ethylene loss is identified as the lowest energy reaction channel. Dehydrogenation is found to result from step-wise H atom loss. Isomerization via disproportionation is also identified as a primary reaction channel
Optimal control of bond selectivity in unimolecular reactions
International Nuclear Information System (INIS)
Shi Shenghua; Rabitz, H.
1991-01-01
The optimal control theory approach to designing optimal fields for bond-selective unimolecular reactions is presented. A set of equations for determining the optimal fields, which will lead to the achievement of the objective of bond-selective dissociation is developed. The numerical procedure given for solving these equations requires the repeated calculation of the time propagator for the system with the time-dependent Hamiltonian. The splitting approximation combined with the fast Fourier transform algorithm is used for computing the short time propagator. As an illustrative example, a model linear triatomic molecule is treated. The model system consists of two Morse oscillators coupled via kinetic coupling. The magnitude of the dipoles of the two Morse oscillators are the same, the fundamental frequencies are almost the same, but the dissociation energies are different. The rather demanding objective under these conditions is to break the stronger bond while leaving the weaker one intact. It is encouraging that the present computational method efficiently gives rise to the optimal field, which leads to the excellent achievement of the objective of bond selective dissociation. (orig.)
Rate-distortion theory and human perception.
Sims, Chris R
2016-07-01
The fundamental goal of perception is to aid in the achievement of behavioral objectives. This requires extracting and communicating useful information from noisy and uncertain sensory signals. At the same time, given the complexity of sensory information and the limitations of biological information processing, it is necessary that some information must be lost or discarded in the act of perception. Under these circumstances, what constitutes an 'optimal' perceptual system? This paper describes the mathematical framework of rate-distortion theory as the optimal solution to the problem of minimizing the costs of perceptual error subject to strong constraints on the ability to communicate or transmit information. Rate-distortion theory offers a general and principled theoretical framework for developing computational-level models of human perception (Marr, 1982). Models developed in this framework are capable of producing quantitatively precise explanations for human perceptual performance, while yielding new insights regarding the nature and goals of perception. This paper demonstrates the application of rate-distortion theory to two benchmark domains where capacity limits are especially salient in human perception: discrete categorization of stimuli (also known as absolute identification) and visual working memory. A software package written for the R statistical programming language is described that aids in the development of models based on rate-distortion theory. Copyright © 2016 The Author. Published by Elsevier B.V. All rights reserved.
Mixed quantum-classical studies of energy partitioning in unimolecular chemical reactions
Bladow, Landon Lowell
A mixed quantum-classical reaction path Hamiltonian method is utilized to study the dynamics of unimolecular reactions. The method treats motion along the reaction path classically and treats the transverse vibrations quantum mechanically. The theory leads to equations that predict the disposai of the exit-channel potential energy to product translation and vibration. In addition, vibrational state distributions are obtained for the product normal modes. Vibrational excitation results from the curvature of the minimum energy reaction path. The method is applied to six unimolecular reactions: HF elimination from fluoroethane, 1,1-difluoroethane, 1,1-difluoroethene, and trifluoromethane; and HCl elimination from chloroethane and acetyl chloride. The minimum energy paths were calculated at either the MP2 or B3LYP level of theory. In all cases, the majority of the vibrational excitation of the products occurs in the HX fragment. The results are compared to experimental data and other theoretical results, where available. The best agreement between the experimental and calculated HX vibrational distributions is found for the halogenated ethanes, and the experimental deduction that the majority of the HX vibrational excitation arises from the potential energy release is supported. It is believed that the excess energy provided in experiments contributes to the poorer agreement between experiment and theory observed for HF elimination from 1,1-difluoroethene and trifluoromethane. An attempt is described to incorporate a treatment of the excess energy into the present method. However, the sign of the curvature coupling elements is then found to affect the dynamics. Overall, the method appears to be an efficient dynamical tool for modeling the disposal of the exit-channel potential energy in unimolecular reactions.
Furfural: The Unimolecular Dissociative Photoionization Mechanism of the Simplest Furanic Aldehyde.
Winfough, Matthew; Voronova, Krisztina; Muller, Giel; Laguisma, Gabrielle; Sztáray, Bálint; Bodi, Andras; Meloni, Giovanni
2017-05-11
The unimolecular dissociation reactions of energy-selected furfural cations have been studied by imaging photoelectron photoion coincidence spectroscopy at the vacuum-ultraviolet (VUV) beamline of the Swiss Light Source. In the photon energy range of 10.9-14.5 eV, furfural ions decay by numerous fragmentation channels. Modeling the breakdown diagram yielded the 0 K appearance energies of 10.95 ± 0.10, 11.16, and 12.03 eV for the c-C 4 H 3 O-CO + (m/z = 95), c-C 4 H 4 O + (m/z = 68), and c-C 3 H 3 + (m/z = 39) fragment ions, respectively, formed by parallel dissociation channels. An internal conversion from the A″ to the A' electronic state via a conical intersection takes place along the reaction coordinate in the case of the H-loss channel (c-C 4 H 3 O-CO + formation). Quantum chemical calculations and experimental results confirmed a fast conversion to the A' state and that the rate-determining step is a tight transition state on the potential energy surface. Appearance energies were also derived for the sequential dissociation products from the furan cation, c-C 4 H 4 O + , for the formation of CH 2 CO + (m/z = 42), C 3 H 4 + (m/z = 40), and CHO + (m/z = 29) at 12.81, 12.80, and 13.34 eV, respectively. Statistical rate theory modeling of the breakdown diagram can also be used to predict the fractional ion abundances and thermal shifts in mass spectrometric pyrolysis studies to help assigning the m/z channels either to ionization of the neutrals or to dissociative ionization processes, with potential use for combustion diagnostics. The cationic geometry optimizations yielded functional-dependent spurious DFT minima and a deviating planar MP2 optimized geometry, which are briefly discussed.
Multiphoton dissociation and thermal unimolecular reactions induced by infrared lasers
International Nuclear Information System (INIS)
Dai, H.L.
1981-04-01
Multiphoton dissociation (MPD) of ethyl chloride was studied using a tunable 3.3 μm laser to excite CH stretches. The absorbed energy increases almost linearly with fluence, while for 10 μm excitation there is substantial saturation. Much higher dissociation yields were observed for 3.3 μm excitation than for 10 μm excitation, reflecting bottlenecking in the discrete region of 10 μm excitation. The resonant nature of the excitation allows the rate equations description for transitions in the quasicontinuum and continuum to be extended to the discrete levels. Absorption cross sections are estimated from ordinary ir spectra. A set of cross sections which is constant or slowly decreasing with increasing vibrational excitation gives good fits to both absorption and dissociation yield data. The rate equations model was also used to quantitatively calculate the pressure dependence of the MPD yield of SF 6 caused by vibrational self-quenching. Between 1000-3000 cm -1 of energy is removed from SF 6 excited to approx. > 60 kcal/mole by collision with a cold SF 6 molecule at gas kinetic rate. Calculation showed the fluence dependence of dissociation varies strongly with the gas pressure. Infrared multiphoton excitation was applied to study thermal unimolecular reactions. With SiF 4 as absorbing gas for the CO 2 laser pulse, transient high temperature pulses were generated in a gas mixture. IR fluorescence from the medium reflected the decay of the temperature. The activation energy and the preexponential factor of the reactant dissociation were obtained from a phenomenological model calculation. Results are presented in detail
On the theory of interest rate policy
Directory of Open Access Journals (Sweden)
Heinz-Peter Spahn
2001-12-01
Full Text Available A new consensus in the theory of monetary policy has been reached pointing to the pivotal role of interest rates that are set in accordance with central banks' reaction functions. The decisive criterion of assessing the Taylor rule, inflation and monetary targeting is not the macrotheoretic foundation of these concepts. They serve as "languages" coordinating heterogeneous beliefs among policy makers and private agents, and should also allow rule-based discretionary policies when markets are in need of leadership. Contrary to the ECB dogma, the Fed is right to have an eye on the risks of inflation and unemployment.
Scalable synthesis of sequence-defined, unimolecular macromolecules by Flow-IEG
Leibfarth, Frank A.; Johnson, Jeremiah A.; Jamison, Timothy F.
2015-01-01
We report a semiautomated synthesis of sequence and architecturally defined, unimolecular macromolecules through a marriage of multistep flow synthesis and iterative exponential growth (Flow-IEG). The Flow-IEG system performs three reactions and an in-line purification in a total residence time of under 10 min, effectively doubling the molecular weight of an oligomeric species in an uninterrupted reaction sequence. Further iterations using the Flow-IEG system enable an exponential increase in molecular weight. Incorporating a variety of monomer structures and branching units provides control over polymer sequence and architecture. The synthesis of a uniform macromolecule with a molecular weight of 4,023 g/mol is demonstrated. The user-friendly nature, scalability, and modularity of Flow-IEG provide a general strategy for the automated synthesis of sequence-defined, unimolecular macromolecules. Flow-IEG is thus an enabling tool for theory validation, structure–property studies, and advanced applications in biotechnology and materials science. PMID:26269573
Chang, Xiaoyen Y.; Sewell, Thomas D.; Raff, Lionel M.; Thompson, Donald L.
1992-11-01
The possibility of utilizing different types of power spectra obtained from classical trajectories as a diagnostic tool to identify the presence of nonstatistical dynamics is explored by using the unimolecular bond-fission reactions of 1,2-difluoroethane and the 2-chloroethyl radical as test cases. In previous studies, the reaction rates for these systems were calculated by using a variational transition-state theory and classical trajectory methods. A comparison of the results showed that 1,2-difluoroethane is a nonstatistical system, while the 2-chloroethyl radical behaves statistically. Power spectra for these two systems have been generated under various conditions. The characteristics of these spectra are as follows: (1) The spectra for the 2-chloroethyl radical are always broader and more coupled to other modes than is the case for 1,2-difluoroethane. This is true even at very low levels of excitation. (2) When an internal energy near or above the dissociation threshold is initially partitioned into a local C-H stretching mode, the power spectra for 1,2-difluoroethane broaden somewhat, but discrete and somewhat isolated bands are still clearly evident. In contrast, the analogous power spectra for the 2-chloroethyl radical exhibit a near complete absence of isolated bands. The general appearance of the spectrum suggests a very high level of mode-to-mode coupling, large intramolecular vibrational energy redistribution (IVR) rates, and global statistical behavior. (3) The appearance of the power spectrum for the 2-chloroethyl radical is unaltered regardless of whether the initial C-H excitation is in the CH2 or the CH2Cl group. This result also suggests statistical behavior. These results are interpreted to mean that power spectra may be used as a diagnostic tool to assess the statistical character of a system. The presence of a diffuse spectrum exhibiting a nearly complete loss of isolated structures indicates that the dissociation dynamics of the molecule will
Raff, Lionel M.
1989-06-01
The unimolecular decomposition reactions of 1,2-difluoroethane upon mode-specific excitation to a total internal energy of 7.5 eV are investigated using classical trajectory methods and a previously formulated empirical potential-energy surface. The decomposition channels for 1,2-difluoroethane are, in order of importance, four-center HF elimination, C-C bond rupture, and hydrogen-atom dissociation. This order is found to be independent of the particular vibrational mode excited. Neither fluorine-atom nor F2 elimination reactions are ever observed even though these dissociation channels are energetically open. For four-center HF elimination, the average fraction of the total energy partitioned into internal HF motion varies between 0.115-0.181 depending upon the particular vibrational mode initially excited. The internal energy of the fluoroethylene product lies in the range 0.716-0.776. Comparison of the present results with those previously obtained for a random distribution of the initial 1,2-difluoroethane internal energy [J. Phys. Chem. 92, 5111 (1988)], shows that numerous mode-specific effects are present in these reactions in spite of the fact that intramolecular energy transfer rates for this system are 5.88-25.5 times faster than any of the unimolecular reaction rates. Mode-specific excitation always leads to a total decomposition rate significantly larger than that obtained for a random distribution of the internal energy. Excitation of different 1,2-difluoroethane vibrational modes is found to produce as much as a 51% change in the total decomposition rate. Mode-specific effects are also seen in the product energy partitioning. The rate coefficients for decomposition into the various channels are very sensitive to the particular mode excited. A comparison of the calculated mode-specific effects with the previously determined mode-to-mode energy transfer rate coefficients [J. Chem. Phys. 89, 5680 (1988)] shows that, to some extent, the presence of mode
Alquaity, Awad B. S.; Giri, Binod Raj; Lo, John M.H.; Farooq, Aamir
2015-01-01
Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775-1082 K and pressures near 900 Torr using a high-repetition rate time of flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly, and it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration-time histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the falloff behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ, and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies of the stationary points were calculated using coupled cluster with single and double excitations including the perturbative treatment of triple excitation (CCSD(T)) level of theory. It was found that the dissociation occurs via a concerted mechanism requiring an energy barrier of 48.3 kcal/mol to be overcome. The new experimental data and theoretical calculations serve as a validation and extension of kinetic data published earlier by other groups. Calculated values for the pressure limiting rate coefficient can be expressed as log10 k∞ (s-1) = [15.84 - (49.54 (kcal/mol)/2.3RT)] (500-1400 K). © 2015 American Chemical Society.
Alquaity, Awad B. S.
2015-05-15
Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775-1082 K and pressures near 900 Torr using a high-repetition rate time of flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly, and it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration-time histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the falloff behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ, and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies of the stationary points were calculated using coupled cluster with single and double excitations including the perturbative treatment of triple excitation (CCSD(T)) level of theory. It was found that the dissociation occurs via a concerted mechanism requiring an energy barrier of 48.3 kcal/mol to be overcome. The new experimental data and theoretical calculations serve as a validation and extension of kinetic data published earlier by other groups. Calculated values for the pressure limiting rate coefficient can be expressed as log10 k∞ (s-1) = [15.84 - (49.54 (kcal/mol)/2.3RT)] (500-1400 K). © 2015 American Chemical Society.
Grajales Gonzalez, Edwing Javier
2018-05-01
The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with their favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular and H-assisted tautomerism of propen-2-ol to acetone, which are included in butanol combustion kinetic models, are assigned rate parameters based on the analogous unimolecular tautomerism vinyl alcohol ↔ acetaldehyde and H addition to the double bound of iso-butene, respectively. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the unimolecular and H-assisted tautomerism, i-C3H5OH⟺CH3COCH3 and i-C3H5OH+Ḣ⟺CH3COCH3+Ḣ, was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) and CCSD(T)/aug-cc-pVTZ//M062X/cc-pVTZ ab initio calculations, respectively. For H-assisted tautomerism, the reaction takes place in two consecutive steps: i-C3H5OH+Ḣ⟺CH3ĊOHCH3 and CH3ĊOHCH3⟺CH3COCH3+Ḣ. Multistructural torsional anharmonicity and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both isomerizations. Results for unimolecular tautomerism differ from vinyl alcohol ↔ acetaldehyde analogue reactions, which shows lower rate constant values. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed unimolecular rate constants showed important differences in comparison with previous results, such as larger acetone yield and
Abou-Zied, Osama K.; McDonald, J. Douglas
1998-07-01
The bimolecular reaction of O(3P) with ethylene and the unimolecular photodissociation of acetaldehyde and formaldehyde have been studied using a picosecond pump/probe technique. The bimolecular reaction was initiated in a van der Waals dimer precursor, C2H4ṡNO2, and the evolution of the vinoxy radical product monitored by laser-induced fluorescence. The NO2 constituent of the complex was photodissociated at 266 nm. The triplet oxygen atom then attacks a carbon atom of C2H4 to form a triplet diradical (CH2CH2O) which subsequently dissociates to vinoxy (CH2CHO) and H. The rise time of vinoxy radical production was measured to be 217 (+75-25) ps. RRKM theory was applied and a late high exit barrier was invoked in order to fit the measured rise time. The structure and binding energy of the van der Waals complex have been modeled using Lennard-Jones type potentials and the results were compared with other systems. The unimolecular side of the potential energy surfaces of this reaction has been investigated by photodissociating acetaldehyde at the same pump energy of 266 nm. The resulting photoproducts, acetyl radical (CH3CO) and formyl radical (HCO), have been monitored by resonance enhanced multiphoton ionization (REMPI) combined with a time-of-flight mass spectrometer. The similarity in the measured evolution times of both radicals indicates the same photodissociation pathway of the parent molecule. The photodissociation rate of acetaldehyde is estimated from RRKM theory to be very fast (3×1012s-1). The T1←S1 intersystem crossing (ISC) rate is found to be the rate determining step to photodissociation and increases with energy. The REMPI mechanism for the production of CH3CO+ is proposed to be the same as that of HCO+(2+1). The HCO product from the photodissociation of formaldehyde at 266 nm reveals a faster T1←S1 ISC rate than in acetaldehyde.
Growth rate, population entropy, and perturbation theory.
Demetrius, L.
1989-01-01
This paper is concerned with the connection between two classes of population variables: measures of population growth rate—the Malthusian parameter, the net reproduction rate, the gross reproduction rate, and the mean life expectancy; and measures of demographic heterogeneity—population entropy. It is shown that the entropy functions predict the response of the growth rate parameters to perturbations in the age-specific fecundity and mortality schedule. These results are invoked to introduce...
Chartist Trading in Exchange Rate Theory
Selander, Carina
2006-01-01
This thesis consists of four papers, of which paper 1 and 4 are co-written with Mikael Bask. Paper [1] implements chartists trading in a sticky-price monetary model for determining the exchange rate. It is demonstrated that chartists cause the exchange rate to "overshoot the overshooting equilibrium" of a sticky-price monetary model. Chartists base their trading on a short-long moving average. The importance of technical trading depends inversely on the time horizon in currency trade. The exc...
International Nuclear Information System (INIS)
Farneth, W.E.; Thomsen, M.W.
1982-01-01
The infrared photochemistry of bicyclopropyl yields product mixtures that are not easily rationalized on the basis of the mechanistic scheme suggested by previous pyrolysis work. As a result of this inconsistency the thermal chemistry of bicyclopropyl and analogues deuterated specifically on one ring has been reexamined. A significant new reaction channel involving the chemically activated decomposition of cyclohexene to ethylene and butadiene has been demonstrated. Evidence for the involvement of chemically activated cyclohexene is as follows: (1) isotopic labeling studies implying a symmetric intermediate, (2) a pressure-dependent ratio of cyclohexene to butadiene and ethylene, (3) good agreement between experimental and calculated values for the unimolecular rate constant for retro-Diels-Alder decay of ''hot'' cyclohexene. A comprehensive mechanism for the unimolecular decay of bicyclopropyl is proposed. The important elements of this mechanism are a single first-formed 1,3 biradical common to all products and the intervention of chemical activation in the generation of several of the secondary products
Rate Theory for Correlated Processes: Double Jumps in Adatom Diffusion
DEFF Research Database (Denmark)
Jacobsen, J.; Jacobsen, Karsten Wedel; Sethna, J.
1997-01-01
We study the rate of activated motion over multiple barriers, in particular the correlated double jump of an adatom diffusing on a missing-row reconstructed platinum (110) surface. We develop a transition path theory, showing that the activation energy is given by the minimum-energy trajectory...... which succeeds in the double jump. We explicitly calculate this trajectory within an effective-medium molecular dynamics simulation. A cusp in the acceptance region leads to a root T prefactor for the activated rate of double jumps. Theory and numerical results agree....
Grajales Gonzalez, Edwing
2018-03-21
The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with its favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Enols are important intermediates in the combustion of C4 alcohols, as well as in atmospheric processes. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular tautomerism of propen-2-ol ↔ acetone, which is included in butanol combustion kinetic models, is assigned rate parameters based on the tautomerism vinyl alcohol ↔ acetaldehyde as an analogy. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the titled reaction was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) ab initio calculations, with multistructural torsional anharmonicity and variational transition state theory considerations in a wide temperature and pressure range (200-3000 K; 0.1-108 kPa). Results differ from vinyl alcohol ↔ acetaldehyde analogue reaction, which shows lower rate constant values. It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.
Grajales Gonzalez, Edwing Javier; Monge Palacios, Manuel; Sarathy, Mani
2018-01-01
The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with its favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Enols are important intermediates in the combustion of C4 alcohols, as well as in atmospheric processes. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular tautomerism of propen-2-ol ↔ acetone, which is included in butanol combustion kinetic models, is assigned rate parameters based on the tautomerism vinyl alcohol ↔ acetaldehyde as an analogy. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the titled reaction was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) ab initio calculations, with multistructural torsional anharmonicity and variational transition state theory considerations in a wide temperature and pressure range (200-3000 K; 0.1-108 kPa). Results differ from vinyl alcohol ↔ acetaldehyde analogue reaction, which shows lower rate constant values. It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption.
Mechanism of Strain Rate Effect Based on Dislocation Theory
International Nuclear Information System (INIS)
Kun, Qin; Shi-Sheng, Hu; Li-Ming, Yang
2009-01-01
Based on dislocation theory, we investigate the mechanism of strain rate effect. Strain rate effect and dislocation motion are bridged by Orowan's relationship, and the stress dependence of dislocation velocity is considered as the dynamics relationship of dislocation motion. The mechanism of strain rate effect is then investigated qualitatively by using these two relationships although the kinematics relationship of dislocation motion is absent due to complicated styles of dislocation motion. The process of strain rate effect is interpreted and some details of strain rate effect are adequately discussed. The present analyses agree with the existing experimental results. Based on the analyses, we propose that strain rate criteria rather than stress criteria should be satisfied when a metal is fully yielded at a given strain rate. (condensed matter: structure, mechanical and thermal properties)
Divided Saddle Theory: A New Idea for Rate Constant Calculation.
Daru, János; Stirling, András
2014-03-11
We present a theory of rare events and derive an algorithm to obtain rates from postprocessing the numerical data of a free energy calculation and the corresponding committor analysis. The formalism is based on the division of the saddle region of the free energy profile of the rare event into two adjacent segments called saddle domains. The method is built on sampling the dynamics within these regions: auxiliary rate constants are defined for the saddle domains and the absolute forward and backward rates are obtained by proper reweighting. We call our approach divided saddle theory (DST). An important advantage of our approach is that it requires only standard computational techniques which are available in most molecular dynamics codes. We demonstrate the potential of DST numerically on two examples: rearrangement of alanine-dipeptide (CH3CO-Ala-NHCH3) conformers and the intramolecular Cope reaction of the fluxional barbaralane molecule.
Kinetic aspects of the embedded clusters: Reaction - Rate Theory
International Nuclear Information System (INIS)
Despa, F.; Apostol, M.
1995-07-01
The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs
Benchmark calculations of thermal reaction rates. I - Quantal scattering theory
Chatfield, David C.; Truhlar, Donald G.; Schwenke, David W.
1991-01-01
The thermal rate coefficient for the prototype reaction H + H2 yields H2 + H with zero total angular momentum is calculated by summing, averaging, and numerically integrating state-to-state reaction probabilities calculated by time-independent quantum-mechanical scattering theory. The results are very carefully converged with respect to all numerical parameters in order to provide high-precision benchmark results for confirming the accuracy of new methods and testing their efficiency.
Turpin, Martha A; Smith, Kylie C; Heard, George L; Setser, D W; Holmes, Bert E
2014-10-09
The recombination of CCl3 radicals with CH3, CH3CH2, and CF3CH2 radicals was used to generate CH3CCl3, CH3CH2CCl3, and CF3CH2CCl3 molecules with approximately 87 kcal mol(-1) of vibrational energy in a bath gas at room temperature. The competition between collisional deactivation and unimolecular reaction by HCl elimination was used to obtain the experimental rate constants for each molecule. These experimental rate constants were matched to calculated statistical unimolecular rate constants to assign threshold energies to the three HCl elimination reactions. The models needed for the calculations of the rate constants were obtained from molecular structure calculations using density functional theory (DFT) with the hybrid density-functional MO6-2X recommended by Truhlar for transition states. The assigned threshold energies are 52 ± 2, 50 ± 2, and 52 ± 2 kcal mol(-1) for CH3CCl3, CH3CH2CCl3, and CF3CH2CCl3, respectively, and the CH3 and CF3 groups have only a minor effect on the threshold energies for HCl elimination. The DFT calculated threshold energies are in agreement with the experimentally assigned values. The addition of Cl atoms to the same carbon atom lowers the threshold energy for HCl elimination in the CH3CH2Cl, CH3CHCl2, and CH3CCl3 series. This trend, which is the opposite of that for CH3CH2F, CH3CHF2, and CH3CF3, is discussed in terms of transition-state structure and correlated with the relative stabilities of CH3CH2(+), CH3CHCl(+), and CH3CCl2(+) ions; the relative stabilities are based on the hydride affinities obtained from calculations. Comparison of the reactions of CH3CCl3 and CH2ClCHCl2 shows that the threshold energy is much higher for the isomer with chlorine atoms on both carbon atoms.
Efficiency and credit ratings: a permutation-information-theory analysis
International Nuclear Information System (INIS)
Bariviera, Aurelio Fernandez; Martinez, Lisana B; Zunino, Luciano; Belén Guercio, M; Rosso, Osvaldo A
2013-01-01
The role of credit rating agencies has been under severe scrutiny after the subprime crisis. In this paper we explore the relationship between credit ratings and informational efficiency of a sample of thirty nine corporate bonds of US oil and energy companies from April 2008 to November 2012. For this purpose we use a powerful statistical tool, relatively new in the financial literature: the complexity–entropy causality plane. This representation space allows us to graphically classify the different bonds according to their degree of informational efficiency. We find that this classification agrees with the credit ratings assigned by Moody’s. In particular, we detect the formation of two clusters, which correspond to the global categories of investment and speculative grades. Regarding the latter cluster, two subgroups reflect distinct levels of efficiency. Additionally, we also find an intriguing absence of correlation between informational efficiency and firm characteristics. This allows us to conclude that the proposed permutation-information-theory approach provides an alternative practical way to justify bond classification. (paper)
Bao, Junwei Lucas; Zhang, Xin
2016-01-01
Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727
Random walk theory and exchange rate dynamics in transition economies
Directory of Open Access Journals (Sweden)
Gradojević Nikola
2010-01-01
Full Text Available This paper investigates the validity of the random walk theory in the Euro-Serbian dinar exchange rate market. We apply Andrew Lo and Archie MacKinlay's (1988 conventional variance ratio test and Jonathan Wright's (2000 non-parametric ranks and signs based variance ratio tests to the daily Euro/Serbian dinar exchange rate returns using the data from January 2005 - December 2008. Both types of variance ratio tests overwhelmingly reject the random walk hypothesis over the data span. To assess the robustness of our findings, we examine the forecasting performance of a non-linear, nonparametric model in the spirit of Francis Diebold and James Nason (1990 and find that it is able to significantly improve upon the random walk model, thus confirming the existence of foreign exchange market imperfections in a small transition economy such as Serbia. In the last part of the paper, we conduct a comparative study on how our results relate to those of other transition economies in the region.
Adult Attachment Ratings (AAR): an item response theory analysis.
Pilkonis, Paul A; Kim, Yookyung; Yu, Lan; Morse, Jennifer Q
2014-01-01
The Adult Attachment Ratings (AAR) include 3 scales for anxious, ambivalent attachment (excessive dependency, interpersonal ambivalence, and compulsive care-giving), 3 for avoidant attachment (rigid self-control, defensive separation, and emotional detachment), and 1 for secure attachment. The scales include items (ranging from 6-16 in their original form) scored by raters using a 3-point format (0 = absent, 1 = present, and 2 = strongly present) and summed to produce a total score. Item response theory (IRT) analyses were conducted with data from 414 participants recruited from psychiatric outpatient, medical, and community settings to identify the most informative items from each scale. The IRT results allowed us to shorten the scales to 5-item versions that are more precise and easier to rate because of their brevity. In general, the effective range of measurement for the scales was 0 to +2 SDs for each of the attachment constructs; that is, from average to high levels of attachment problems. Evidence for convergent and discriminant validity of the scales was investigated by comparing them with the Experiences of Close Relationships-Revised (ECR-R) scale and the Kobak Attachment Q-sort. The best consensus among self-reports on the ECR-R, informant ratings on the ECR-R, and expert judgments on the Q-sort and the AAR emerged for anxious, ambivalent attachment. Given the good psychometric characteristics of the scale for secure attachment, however, this measure alone might provide a simple alternative to more elaborate procedures for some measurement purposes. Conversion tables are provided for the 7 scales to facilitate transformation from raw scores to IRT-calibrated (theta) scores.
Photoionization cross sections and Auger rates calculated by many-body perturbation theory
International Nuclear Information System (INIS)
Kelly, H.P.
1976-01-01
Methods for applying the many body perturbation theory to atomic calculations are discussed with particular emphasis on calculation of photoionization cross sections and Auger rates. Topics covered include: Rayleigh--Schroedinger theory; many body perturbation theory; calculations of photoionization cross sections; and Auger rates
Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice
2012-10-30
Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH. Copyright © 2012 Wiley Periodicals, Inc.
DEFF Research Database (Denmark)
Vegge, Tejs
2004-01-01
The dissociation of molecular hydrogen on a Mgs0001d surface and the subsequent diffusion of atomic hydrogen into the magnesium substrate is investigated using Density Functional Theory (DFT) calculations and rate theory. The minimum energy path and corresponding transition states are located usi...... to be rate-limiting for the ab- and desorption of hydrogen, respectively. Zero-point energy contributions are found to be substantial for the diffusion of atomic hydrogen, but classical rates are still found to be within an order of magnitude at room temperature.......The dissociation of molecular hydrogen on a Mgs0001d surface and the subsequent diffusion of atomic hydrogen into the magnesium substrate is investigated using Density Functional Theory (DFT) calculations and rate theory. The minimum energy path and corresponding transition states are located using...
International Nuclear Information System (INIS)
Rabia, M.A.; Fahmy, M.A.
1992-01-01
The kinetic energy released during seven unimolecular ionic transitions, generated from benzyl alcohol and benzyl amine have been studied as a function of ion source temperature and ionizing electron energy. Only, the kinetic energy released during H CN elimination from fragment [C 7 H 8 N]+ ion of benzyl amine displays a temperature dependence. For only two transitions, generated from benzyl alcohol, the kinetic energy released show a significant ionizing electron energy dependence. These results may reveal the role of the internal energy of reacting ions in producing the kinetic energy released some transitions produced from benzyl alcohol
Exchange rate determination and the flaws of mainstream monetary theory
Directory of Open Access Journals (Sweden)
HEINER FLASSBECK
2018-03-01
Full Text Available ABSTRACT Developing countries in general need flexibility and a sufficient number of instruments to prevent excessive volatility. Evidence does not support the orthodox belief that, with free floating, international financial markets will perform that role by smoothly adjusting exchange rates to their “equilibrium” level. In reality, exchange rates under a floating regime have proved to be highly unstable, leading to long spells of misalignment. The experience with hard pegs has not been satisfactory either: the exchange rate could not be corrected in cases of external shocks or misalignment. Given this experience, “intermediate” regimes are preferable when there is instability in international financial markets.
Putting Reaction Rates and Collision Theory in the Hands of Your Students.
Evenson, Andy
2002-01-01
Describes a simulation that can be used to give concrete analogies of collision theory and the factors that affect reaction rates including temperature, concentration, catalyst, and molecular orientation. The simulation works best if done as an introduction to the concepts to help prevent misconceptions about reaction rates and collision theory.…
THE EVOLUTION OF CURRENCY RELATIONS IN THE LIGHT OF MAJOR EXCHANGE RATE ADJUSTMENT THEORIES
Directory of Open Access Journals (Sweden)
Sergiy TKACH
2014-07-01
Full Text Available This paper examines the impact of major exchange rate adjustment theories on the global monetary system. The reasons of the previous organization forms of monetary relations collapse at the global level are defined. The main achievements and failures of major exchange rate theories are described.
Item Response Theory Analyses of the Parent and Teacher Ratings of the DSM-IV ADHD Rating Scale
Gomez, Rapson
2008-01-01
The graded response model (GRM), which is based on item response theory (IRT), was used to evaluate the psychometric properties of the inattention and hyperactivity/impulsivity symptoms in an ADHD rating scale. To accomplish this, parents and teachers completed the DSM-IV ADHD Rating Scale (DARS; Gomez et al., "Journal of Child Psychology and…
Vibrational quasi-continuum in unimolecular multiphoton dissociation
Energy Technology Data Exchange (ETDEWEB)
Garcia Fernandez, P.; Gonzalez-Diaz, P.F.
1987-04-01
The vibrational quasi-continuum of the boron trifluoride molecule has been qualitatively studied and the formalism extended to treat N-normal-mode molecules. The anharmonic potential curves for the BF/sub 3/ normal modes have been calculated, and the computed anharmonicity constants have been tested against the fundamental frequencies. The potential curve of the wagging mode has been simulated by an internal rotation of one of the fluoride atoms. The vibrational-energy levels and wave functions have been calculated applying second-order perturbation theory. The quasi-continuum energy levels of BF/sub 3/ have been obtained by means of a method based in forming adequate linear combinations of wave functions belonging to the N-1 modes resulting from removing the i.r.-active mode;the associated energies have been minimized using a constrained minimization procedure. It has been found that the energy pattern of the N-1 vibrational modes possesses an energy density high enough for constituting a vibrational heat bath and, finally, it has been verified that the ''fictitious'' pattern of the active mode is included in the pattern of the N-1 modes.
Targeting the Real Exchange Rate; Theory and Evidence
Carlos A. Végh Gramont; Guillermo Calvo; Carmen Reinhart
1994-01-01
This paper presents a theoretical and empirical analysis of policies aimed at setting a more depreciated level of the real exchange rate. An intertemporal optimizing model suggests that, in the absence of changes in fiscal policy, a more depreciated level of the real exchange can only be attained temporarily. This can be achieved by means of higher inflation and/or higher real interest rates, depending on the degree of capital mobility. Evidence for Brazil, Chile, and Colombia supports the mo...
Short-run Exchange-Rate Dynamics: Theory and Evidence
DEFF Research Database (Denmark)
Carlson, John A.; Dahl, Christian Møller; Osler, Carol L.
Recent research has revealed a wealth of information about the microeconomics of currency markets and thus the determination of exchange rates at short horizons. This information is valuable to us as scientists since, like evidence of macroeconomic regularities, it can provide critical guidance...... of currency markets, it accurately reflects the constraints and objectives faced by the major participants, and it fits key stylized facts concerning returns and order flow. With respect to macroeconomics, the model is consistent with most of the major puzzles that have emerged under floating rates....
An Application of Durkheim's Theory of Suicide to Prison Suicide Rates in the United States
Tartaro, Christine; Lester, David
2005-01-01
E. Durkheim (1897) suggested that the societal rate of suicide might be explained by societal factors, such as marriage, divorce, and birth rates. The current study examined male prison suicide rates and suicide rates for men in the total population in the United States and found that variables based on Durkheim's theory of suicide explained…
Star polymer-based unimolecular micelles and their application in bio-imaging and diagnosis.
Jin, Xin; Sun, Pei; Tong, Gangsheng; Zhu, Xinyuan
2018-02-03
As a novel kind of polymer with covalently linked core-shell structure, star polymers behave in nanostructure in aqueous medium at all concentration range, as unimolecular micelles at high dilution condition and multi-micelle aggregates in other situations. The unique morphologies endow star polymers with excellent stability and functions, making them a promising platform for bio-application. A variety of functions including imaging and therapeutics can be achieved through rational structure design of star polymers, and the existence of plentiful end-groups on shell offers the opportunity for further modification. In the last decades, star polymers have become an attracting platform on fabrication of novel nano-systems for bio-imaging and diagnosis. Focusing on the specific topology and physicochemical properties of star polymers, we have reviewed recent development of star polymer-based unimolecular micelles and their bio-application in imaging and diagnosis. The main content of this review summarizes the synthesis of integrated architecture of star polymers and their self-assembly behavior in aqueous medium, focusing especially on the recent advances on their bio-imaging application and diagnosis use. Finally, we conclude with remarks and give some outlooks for further exploration in this field. Copyright © 2018 Elsevier Ltd. All rights reserved.
Smith, Caleb A; Gillespie, Blanton R; Heard, George L; Setser, D W; Holmes, Bert E
2017-11-22
The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.
Calculus of variations in rate of reactions tax using the general pertubation theory
International Nuclear Information System (INIS)
Silva, F.C. da.
1981-02-01
A perturbation expression to calculate the variations in the rates of integral parameters (such as reaction rates) of a reactor using a Time-Independent Generalized Perturbation Theory, was developed. This theory makes use of the concepts of neutron generation and neutron importance with respect to a given process occurring in a system. The application of Time-Dependent Generalized Perturbation Theory to the calculation of Burnup, by using the expressions derived by A. Gandini, along with the perturbation expression derived in the Time Independent Generalized Perturbation Theory, is done. (Author) [pt
Effective dynamics along given reaction coordinates, and reaction rate theory.
Zhang, Wei; Hartmann, Carsten; Schütte, Christof
2016-12-22
In molecular dynamics and related fields one considers dynamical descriptions of complex systems in full (atomic) detail. In order to reduce the overwhelming complexity of realistic systems (high dimension, large timescale spread, limited computational resources) the projection of the full dynamics onto some reaction coordinates is examined in order to extract statistical information like free energies or reaction rates. In this context, the effective dynamics that is induced by the full dynamics on the reaction coordinate space has attracted considerable attention in the literature. In this article, we contribute to this discussion: we first show that if we start with an ergodic diffusion process whose invariant measure is unique then these properties are inherited by the effective dynamics. Then, we give equations for the effective dynamics, discuss whether the dominant timescales and reaction rates inferred from the effective dynamics are accurate approximations of such quantities for the full dynamics, and compare our findings to results from approaches like Mori-Zwanzig, averaging, or homogenization. Finally, by discussing the algorithmic realization of the effective dynamics, we demonstrate that recent algorithmic techniques like the "equation-free" approach and the "heterogeneous multiscale method" can be seen as special cases of our approach.
Attaining the rate-independent limit of a rate-dependent strain gradient plasticity theory
DEFF Research Database (Denmark)
El-Naaman, Salim Abdallah; Nielsen, Kim Lau; Niordson, Christian Frithiof
2016-01-01
The existence of characteristic strain rates in rate-dependent material models, corresponding to rate-independent model behavior, is studied within a back stress based rate-dependent higher order strain gradient crystal plasticity model. Such characteristic rates have recently been observed...... for steady-state processes, and the present study aims to demonstrate that the observations in fact unearth a more widespread phenomenon. In this work, two newly proposed back stress formulations are adopted to account for the strain gradient effects in the single slip simple shear case, and characteristic...... rates for a selected quantity are identified through numerical analysis. Evidently, the concept of a characteristic rate, within the rate-dependent material models, may help unlock an otherwise inaccessible parameter space....
"Depletion": A Game with Natural Rules for Teaching Reaction Rate Theory.
Olbris, Donald J.; Herzfeld, Judith
2002-01-01
Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Presents the game with a set of follow-up questions suitable for either a quiz or discussion. Also describes student reaction to the game. (MM)
DEFF Research Database (Denmark)
Nielsen, Kim Lau; Niordson, Christian Frithiof
2014-01-01
of a single plastic zone is analyzed to illustrate the agreement with earlier published results, whereafter examples of (ii) multiple plastic zone interaction, and (iii) elastic–plastic loading/unloading are presented. Here, the simple shear problem of an infinite slab constrained between rigid plates......A numerical model formulation of the higher order flow theory (rate-independent) by Fleck and Willis [2009. A mathematical basis for strain-gradient plasticity theory – part II: tensorial plastic multiplier. Journal of the Mechanics and Physics of Solids 57, 1045-1057.], that allows for elastic–plastic...... loading/unloading and the interaction of multiple plastic zones, is proposed. The predicted model response is compared to the corresponding rate-dependent version of visco-plastic origin, and coinciding results are obtained in the limit of small strain-rate sensitivity. First, (i) the evolution...
Riddles, Cynthia Jeannette
The coatings industry has adapted to more stringent guidelines in paint formulations. Current VOC (volatile organic compound) limits placed by the federal government have pushed the industry toward the development of paint formulations which have very little to no VOC's. The development of Colloidal Unimolecular Polymer (CUP) particles is a step in the direction of providing a resin system which exists in zero VOC aqueous dispersion. The CUP particles are a part of the polymer field of Single Chain Nano Particles (SCNP) and ranged in diameters of 3-9 nm. The research presented in this dissertation describes the synthesis and design of these particles along with the various means of instrumentation used to gain insight into the structure and nature of these particles when suspended in aqueous medium.
Thermal unimolecular decomposition of methanol. Zum thermischen unimolekularen Zerfall von Methanol
Energy Technology Data Exchange (ETDEWEB)
Spindler, K
1979-01-01
The thermal unimolecular decomposition of methanol and that of acetone (1B) were investigated experimentally after reflected shockwaves, by following up the OH and CH/sub 3/ absorption or the CH/sub 3/ and acetone absorption respectively. A computer simulation of the decomposition of methanol and the subsequent reactions was done. This gave velocity constants for some reactions, which are different from those that are found in the literature. The experimental investigation of the decomposition of acetone, from comparison of the results with the data in the literature, shows that the observations of CH/sub 3/ absorption are very suitable for obtaining velocity constants for decomposition reactions, where CH/sub 3/ radicals are formed in the first stage.
International Nuclear Information System (INIS)
Wojnarovits, L.; Foeldiak, G.
1980-01-01
Unimolecular H 2 elimination from alkanes was investigated in cyclopentane-cyclohexane, n-hexane-cyclohexane and cyclohexane-cyclooctane mixtures during fluradiolysis and 7.6 eV photolysis. During the radiolysis of all systems, and when the fluorescence shift law allowed it, during the photolysis as well, inhibited H 2 detachment was observed from the first component and sensitized hydrogen molecule elimination from the second. It has been concluded that the same excited state (the lowest singlet, S 1 ) is responsible for the H 2 elimination during radiolysis and photolysis and this is that one that gives rise to fluorescence in the experiments of other authors. The H 2 and H elimination from alkanes generally have different excited precursors. The direct population of S 1 by γ-irradiation is of limited importance and this intermediate is mainly produced in ''charge neutralization'' processes. (author)
Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane
Directory of Open Access Journals (Sweden)
Afshin Taghva Manesh
2017-02-01
Full Text Available The present work provides quantitative results for the rate constants of unimolecular C–H bond fission reactions in the nitro methane at elevated temperatures up to 2000 K. In fact, there are three different hydrogen atoms in the nitro methane. The potential energy surface for each C–H bond fission reaction of nitro methane was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C–H bond fission channel is a barrierless reaction, we have used variational RRKM theory to predict rate coefficients. By means of calculated rate coefficients at different temperatures, the Arrhenius expression of the channel over the temperature range of 100–2000 K is k(T = 5.9E19∗exp(−56274.6/T.
Prediction on corrosion rate of pipe in nuclear power system based on optimized grey theory
International Nuclear Information System (INIS)
Chen Yonghong; Zhang Dafa; Chen Dengke; Jiang Wei
2007-01-01
For the prediction of corrosion rate of pipe in nuclear power system, the pre- diction error from the grey theory is greater, so a new method, optimized grey theory was presented in the paper. A comparison among predicted results from present and other methods was carried out, and it is seem that optimized grey theory is correct and effective for the prediction of corrosion rate of pipe in nuclear power system, and it provides a fundamental basis for the maintenance of pipe in nuclear power system. (authors)
International Nuclear Information System (INIS)
Brannen, J.P.; Wayland, J.R.
1976-01-01
This paper develops a theoretical foundation for the study of biological responses of electric and magnetic fields. The basis of the development is the absolute reaction rate theory and the effects of fields on reaction rates. A simple application to the response of Bacillus subtilis var niger in a microwave field is made. Potential areas of application are discussed
A quantitative theory of solid tumor growth, metabolic rate and vascularization.
Directory of Open Access Journals (Sweden)
Alexander B Herman
Full Text Available The relationships between cellular, structural and dynamical properties of tumors have traditionally been studied separately. Here, we construct a quantitative, predictive theory of solid tumor growth, metabolic rate, vascularization and necrosis that integrates the relationships between these properties. To accomplish this, we develop a comprehensive theory that describes the interface and integration of the tumor vascular network and resource supply with the cardiovascular system of the host. Our theory enables a quantitative understanding of how cells, tissues, and vascular networks act together across multiple scales by building on recent theoretical advances in modeling both healthy vasculature and the detailed processes of angiogenesis and tumor growth. The theory explicitly relates tumor vascularization and growth to metabolic rate, and yields extensive predictions for tumor properties, including growth rates, metabolic rates, degree of necrosis, blood flow rates and vessel sizes. Besides these quantitative predictions, we explain how growth rates depend on capillary density and metabolic rate, and why similar tumors grow slower and occur less frequently in larger animals, shedding light on Peto's paradox. Various implications for potential therapeutic strategies and further research are discussed.
Phenomenological rate process theory for the storage of atomic H in solid Hsub(2)sup(*)
International Nuclear Information System (INIS)
Rosen, G.
1976-01-01
A phenomenological rate process theory is developed for the storage and rapid recombination of atomic hydrogen fuel radical in a crystalline molecular hydrogen solid at temperatures in the range o.1K(<=)T(<=K. It is shown that such a theory can account quantitatively for the recently observed dependence of the storage time on the storage temperature, for the maximum concentration of trapped H atom, and for the time duration of the energy release in the tritium decay experiments of Webeler
General Theory of Decoy-State Quantum Cryptography with Dark Count Rate Fluctuation
International Nuclear Information System (INIS)
Xiang, Gao; Shi-Hai, Sun; Lin-Mei, Liang
2009-01-01
The existing theory of decoy-state quantum cryptography assumes that the dark count rate is a constant, but in practice there exists fluctuation. We develop a new scheme of the decoy state, achieve a more practical key generation rate in the presence of fluctuation of the dark count rate, and compare the result with the result of the decoy-state without fluctuation. It is found that the key generation rate and maximal secure distance will be decreased under the influence of the fluctuation of the dark count rate
Dark matter relics and the expansion rate in scalar-tensor theories
Energy Technology Data Exchange (ETDEWEB)
Dutta, Bhaskar; Jimenez, Esteban [Mitchell Institute for Fundamental Physics and Astronomy, Department of Physics and Astronomy, Texas A and M University, College Station, TX 77843 (United States); Zavala, Ivonne, E-mail: dutta@physics.tamu.edu, E-mail: este1985@physics.tamu.edu, E-mail: e.i.zavalacarrasco@swansea.ac.uk [Department of Physics, Swansea University, Singleton Park, Swansea, SA2 8PP (United Kingdom)
2017-06-01
We study the impact of a modified expansion rate on the dark matter relic abundance in a class of scalar-tensor theories. The scalar-tensor theories we consider are motivated from string theory constructions, which have conformal as well as disformally coupled matter to the scalar. We investigate the effects of such a conformal coupling to the dark matter relic abundance for a wide range of initial conditions, masses and cross-sections. We find that exploiting all possible initial conditions, the annihilation cross-section required to satisfy the dark matter content can differ from the thermal average cross-section in the standard case. We also study the expansion rate in the disformal case and find that physically relevant solutions require a nontrivial relation between the conformal and disformal functions. We study the effects of the disformal coupling in an explicit example where the disformal function is quadratic.
Engelen, Peter Jan; Lander, Michel W.; van Essen, Marc
Research on crime has by no means reached a definitive conclusion on which factors are related to crime rates. We contribute to the crime literature by providing an integrated empirical model of economic and sociological theories of criminal behavior and by using a very comprehensive set of
Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment
Marcus, R. A.
1964-01-01
In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.
Flenady, Tracy; Dwyer, Trudy; Applegarth, Judith
2017-09-01
Abnormal respiratory rates are one of the first indicators of clinical deterioration in emergency department(ED) patients. Despite the importance of respiratory rate observations, this vital sign is often inaccurately recorded on ED observation charts, compromising patient safety. Concurrently, there is a paucity of research reporting why this phenomenon occurs. To develop a substantive theory explaining ED registered nurses' reasoning when they miss or misreport respiratory rate observations. This research project employed a classic grounded theory analysis of qualitative data. Seventy-nine registered nurses currently working in EDs within Australia. Data collected included detailed responses from individual interviews and open-ended responses from an online questionnaire. Classic grounded theory (CGT) research methods were utilised, therefore coding was central to the abstraction of data and its reintegration as theory. Constant comparison synonymous with CGT methods were employed to code data. This approach facilitated the identification of the main concern of the participants and aided in the generation of theory explaining how the participants processed this issue. The main concern identified is that ED registered nurses do not believe that collecting an accurate respiratory rate for ALL patients at EVERY round of observations is a requirement, and yet organizational requirements often dictate that a value for the respiratory rate be included each time vital signs are collected. The theory 'Rationalising Transgression', explains how participants continually resolve this problem. The study found that despite feeling professionally conflicted, nurses often erroneously record respiratory rate observations, and then rationalise this behaviour by employing strategies that adjust the significance of the organisational requirement. These strategies include; Compensating, when nurses believe they are compensating for errant behaviour by enhancing the patient's outcome
RATING CREATION FOR PROFESSIONAL EDUCATIONAL ORGANIZATIONS BASED ON THE ITEM RESPONSE THEORY
Directory of Open Access Journals (Sweden)
N. E. Erganova
2016-01-01
Full Text Available The aim of the investigation is to theoretically justify and describe approval of the measurement of the level of provision of educational services, education qualities and rating of vocational educational organizations.Methods. The fundamentals of methodology of the research conducted by authors are made by provisions of system approach; research on a schematization and modeling of pedagogical objects; the provision of the theory of measurement of latent variables. As the main methods of research the analysis, synthesis, the comparative analysis, statistical methods of processing of results of research are applied.Results. The paper gives a short comparative analysis of potentials of qualitative approach and strong points of the theory of latent variables in evaluating the quality of education and ratings of the investigated object. The technique of measurement of level of rendering educational services at creation of a rating of the professional educational organizations is stated.Scientific novelty. Pedagogical opportunities of the theory of measurement of latent variables are investigated; the principles of creation of ratings of the professional educational organizations are designated.Practical significance. The operational construct of the latent variable «quality of education» for the secondary professional education (SPE approved in the Perm Territory which can form base of formation of similar constructs for creation of a rating of the professional educational organizations in other regions is developed.
Lera, Sandro Claudio; Sornette, Didier
2018-01-01
A model that combines economic growth rate fluctuations at the microscopic and macroscopic levels is presented. At the microscopic level, firms are growing at different rates while also being exposed to idiosyncratic shocks at the firm and sector levels. We describe such fluctuations as independent Lévy-stable fluctuations, varying over multiple orders of magnitude. These fluctuations are aggregated and measured at the macroscopic level in averaged economic output quantities such as GDP. A fundamental question is thereby to what extent individual firm size fluctuations can have a noticeable impact on the overall economy. We argue that this question can be answered by considering the Lévy fluctuations as embedded in a steep confining potential well, ensuring nonlinear mean-reversal behavior, without having to rely on microscopic details of the system. The steepness of the potential well directly controls the extent to which idiosyncratic shocks to firms and sectors are damped at the level of the economy. Additionally, the theory naturally accounts for business cycles, represented in terms of a bimodal economic output distribution and thus connects two so far unrelated fields in economics. By analyzing 200 years of U.S. gross domestic product growth rates, we find that the model is in good agreement with the data.
Xu, Wenhu; Haule, Kristjan; Kotliar, Gabriel
2013-07-19
We investigate the transport properties of a correlated metal within dynamical mean-field theory. Canonical Fermi liquid behavior emerges only below a very low temperature scale T(FL). Surprisingly the quasiparticle scattering rate follows a quadratic temperature dependence up to much higher temperatures and crosses over to saturated behavior around a temperature scale T(sat). We identify these quasiparticles as constituents of the hidden Fermi liquid. The non-Fermi-liquid transport above T(FL), in particular the linear-in-T resistivity, is shown to be a result of a strongly temperature dependent band dispersion. We derive simple expressions for the resistivity, Hall angle, thermoelectric power and Nernst coefficient in terms of a temperature dependent renormalized band structure and the quasiparticle scattering rate. We discuss possible tests of the dynamical mean-field theory picture of transport using ac measurements.
Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment
Marcus, R. A.
1964-01-01
In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.
Generalized Rate Theory for Void and Bubble Swelling and its Application to Plutonium Metal Alloys
Energy Technology Data Exchange (ETDEWEB)
Allen, P. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Wolfer, W. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2015-10-16
In the classical rate theory for void swelling, vacancies and self-interstitials are produced by radiation in equal numbers, and in addition, thermal vacancies are also generated at the sinks, primarily at edge dislocations, at voids, and at grain boundaries. In contrast, due to the high formation energy of self-interstitials for normal metals and alloys, their thermal generation is negligible, as pointed out by Bullough and Perrin. However, recent DFT calculations of the formation energy of self-interstitial atoms in bcc metals have revealed that the sum of formation and migration energies for self-interstitials atoms (SIA) is of the same order of magnitude as for vacancies. The ratio of the activation energies for thermal generation of SIA and vacancies is presented. For fcc metals, this ratio is around three, but for bcc metals it is around 1.5. Reviewing theoretical predictions of point defect properties in δ-Pu, this ratio could possibly be less than one. As a result, thermal generation of SIA in bcc metals and in plutonium must be taken into considerations when modeling the growth of voids and of helium bubbles, and the classical rate theory (CRT) for void and bubble swelling must be extended to a generalized rate theory (GRT).
Derivation of the chemical-equilibrium rate coefficient using scattering theory
Mickens, R. E.
1977-01-01
Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.
Atkins, Louise; Hunkeler, Enid M; Jensen, Christopher D; Michie, Susan; Lee, Jeffrey K; Doubeni, Chyke A; Zauber, Ann G; Levin, Theodore R; Quinn, Virginia P; Corley, Douglas A
2016-03-01
Interventions to improve physician adenoma detection rates for colonoscopy have generally not been successful, and there are little data on the factors contributing to variation that may be appropriate targets for intervention. We sought to identify factors that may influence variation in detection rates by using theory-based tools for understanding behavior. We separately studied gastroenterologists and endoscopy nurses at 3 Kaiser Permanente Northern California medical centers to identify potentially modifiable factors relevant to physician adenoma detection rate variability by using structured group interviews (focus groups) and theory-based tools for understanding behavior and eliciting behavior change: the Capability, Opportunity, and Motivation behavior model; the Theoretical Domains Framework; and the Behavior Change Wheel. Nine factors potentially associated with adenoma detection rate variability were identified, including 6 related to capability (uncertainty about which types of polyps to remove, style of endoscopy team leadership, compromised ability to focus during an examination due to distractions, examination technique during withdrawal, difficulty detecting certain types of adenomas, and examiner fatigue and pain), 2 related to opportunity (perceived pressure due to the number of examinations expected per shift and social pressure to finish examinations before scheduled breaks or the end of a shift), and 1 related to motivation (valuing a meticulous examination as the top priority). Examples of potential intervention strategies are provided. By using theory-based tools, this study identified several novel and potentially modifiable factors relating to capability, opportunity, and motivation that may contribute to adenoma detection rate variability and be appropriate targets for future intervention trials. Copyright © 2016 American Society for Gastrointestinal Endoscopy. Published by Elsevier Inc. All rights reserved.
International Nuclear Information System (INIS)
Ayala, Orlando; Rosa, Bogdan; Wang Lianping
2008-01-01
The effect of air turbulence on the geometric collision kernel of cloud droplets can be predicted if the effects of air turbulence on two kinematic pair statistics can be modeled. The first is the average radial relative velocity and the second is the radial distribution function (RDF). A survey of the literature shows that no theory is available for predicting the radial relative velocity of finite-inertia sedimenting droplets in a turbulent flow. In this paper, a theory for the radial relative velocity is developed, using a statistical approach assuming that gravitational sedimentation dominates the relative motion of droplets before collision. In the weak-inertia limit, the theory reveals a new term making a positive contribution to the radial relative velocity resulting from a coupling between sedimentation and air turbulence on the motion of finite-inertia droplets. The theory is compared to the direct numerical simulations (DNS) results in part 1, showing a reasonable agreement with the DNS data for bidisperse cloud droplets. For droplets larger than 30 μm in radius, a nonlinear drag (NLD) can also be included in the theory in terms of an effective inertial response time and an effective terminal velocity. In addition, an empirical model is developed to quantify the RDF. This, together with the theory for radial relative velocity, provides a parameterization for the turbulent geometric collision kernel. Using this integrated model, we find that turbulence could triple the geometric collision kernel, relative to the stagnant air case, for a droplet pair of 10 and 20 μm sedimenting through a cumulus cloud at R λ =2x10 4 and ε=600 cm 2 s -3 . For the self-collisions of 20 μm droplets, the collision kernel depends sensitively on the flow dissipation rate
Bailey, Johnathan O; Singleton, Daniel A
2017-11-08
Our previous work found that canonical forms of transition state theory incorrectly predict the regioselectivity of the hydroboration of propene with BH 3 in solution. In response, it has been suggested that alternative statistical and nonstatistical rate theories can adequately account for the selectivity. This paper uses a combination of experimental and theoretical studies to critically evaluate the ability of these rate theories, as well as dynamic trajectories and newly developed localized statistical models, to predict quantitative selectivities and qualitative trends in hydroborations on a broader scale. The hydroboration of a series of terminally substituted alkenes with BH 3 was examined experimentally, and a classically unexpected trend is that the selectivity increases as the alkyl chain is lengthened far from the reactive centers. Conventional and variational transition state theories can predict neither the selectivities nor the trends. The canonical competitive nonstatistical model makes somewhat better predictions for some alkenes but fails to predict trends, and it performs poorly with an alkene chosen to test a specific prediction of the model. Added nonstatistical corrections to this model make the predictions worse. Parametrized Rice-Ramsperger-Kassel-Marcus (RRKM)-master equation calculations correctly predict the direction of the trend in selectivity versus alkene size but overpredict its magnitude, and the selectivity with large alkenes remains unpredictable with any parametrization. Trajectory studies in explicit solvent can predict selectivities without parametrization but are impractical for predicting small changes in selectivity. From a lifetime and energy analysis of the trajectories, "localized RRKM-ME" and "competitive localized noncanonical" rate models are suggested as steps toward a general model. These provide the best predictions of the experimental observations and insight into the selectivities.
Rate Theory Modeling and Simulation of Silicide Fuel at LWR Conditions
Energy Technology Data Exchange (ETDEWEB)
Miao, Yinbin [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Ye, Bei [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Hofman, Gerard [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Yacout, Abdellatif [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Gamble, Kyle [Idaho National Lab. (INL), Idaho Falls, ID (United States). Fuel Modeling and Simulation; Mei, Zhi-Gang [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division
2016-08-29
As a promising candidate for the accident tolerant fuel (ATF) used in light water reactors (LWRs), the fuel performance of uranium silicide (U_{3}Si_{2}) at LWR conditions needs to be well understood. In this report, rate theory model was developed based on existing experimental data and density functional theory (DFT) calculations so as to predict the fission gas behavior in U_{3}Si_{2} at LWR conditions. The fission gas behavior of U_{3}Si_{2} can be divided into three temperature regimes. During steady-state operation, the majority of the fission gas stays in intragranular bubbles, whereas the dominance of intergranular bubbles and fission gas release only occurs beyond 1000 K. The steady-state rate theory model was also used as reference to establish a gaseous swelling correlation of U_{3}Si_{2} for the BISON code. Meanwhile, the overpressurized bubble model was also developed so that the fission gas behavior at LOCA can be simulated. LOCA simulation showed that intragranular bubbles are still dominant after a 70 second LOCA, resulting in a controllable gaseous swelling. The fission gas behavior of U_{3}Si_{2} at LWR conditions is benign according to the rate theory prediction at both steady-state and LOCA conditions, which provides important references to the qualification of U_{3}Si_{2} as a LWR fuel material with excellent fuel performance and enhanced accident tolerance.
International Nuclear Information System (INIS)
Saroukhani, S.; Warner, D.H.
2017-01-01
The rate of thermally activated dislocation motion across a field of solutes is studied using traditional and modern atomistically informed rate theories. First, the accuracy of popular variants of the Harmonic Transition State Theory, as the most common approach, is examined by comparing predictions to direct MD simulations. It is shown that HTST predictions are grossly inaccurate due to the anharmonic effect of thermal softening. Next, the utility of the Transition Interface Sampling was examined as the method was recently shown to be effective for predicting the rate of dislocation-precipitate interactions. For dislocation-solute interactions studied here, TIS is found to be accurate only when the dislocation overcomes multiple obstacles at a time, i.e. jerky motion, and it is inaccurate in the unpinning regime where the energy barrier is of diffusive nature. It is then shown that the Partial Path TIS method - designed for diffusive barriers - provides accurate predictions in the unpinning regime. The two methods are then used to study the temperature and load dependence of the rate. It is shown that Meyer-Neldel (MN) rule prediction of the entropy barrier is not as accurate as it is in the case of dislocation-precipitate interactions. In response, an alternative model is proposed that provides an accurate prediction of the entropy barrier. This model can be combined with TST to offer an attractively simple rate prediction approach. Lastly, (PP)TIS is used to predict the Strain Rate Sensitivity (SRS) factor at experimental strain rates and the predictions are compared to experimental values.
Situated learning theory: adding rate and complexity effects via Kauffman's NK model.
Yuan, Yu; McKelvey, Bill
2004-01-01
For many firms, producing information, knowledge, and enhancing learning capability have become the primary basis of competitive advantage. A review of organizational learning theory identifies two approaches: (1) those that treat symbolic information processing as fundamental to learning, and (2) those that view the situated nature of cognition as fundamental. After noting that the former is inadequate because it focuses primarily on behavioral and cognitive aspects of individual learning, this paper argues the importance of studying learning as interactions among people in the context of their environment. It contributes to organizational learning in three ways. First, it argues that situated learning theory is to be preferred over traditional behavioral and cognitive learning theories, because it treats organizations as complex adaptive systems rather than mere information processors. Second, it adds rate and nonlinear learning effects. Third, following model-centered epistemology, it uses an agent-based computational model, in particular a "humanized" version of Kauffman's NK model, to study the situated nature of learning. Using simulation results, we test eight hypotheses extending situated learning theory in new directions. The paper ends with a discussion of possible extensions of the current study to better address key issues in situated learning.
Characteristics of highly rated leadership in nursing homes using item response theory.
Backman, Annica; Sjögren, Karin; Lindkvist, Marie; Lövheim, Hugo; Edvardsson, David
2017-12-01
To identify characteristics of highly rated leadership in nursing homes. An ageing population entails fundamental social, economic and organizational challenges for future aged care. Knowledge is limited of both specific leadership behaviours and organizational and managerial characteristics which have an impact on the leadership of contemporary nursing home care. Cross-sectional. From 290 municipalities, 60 were randomly selected and 35 agreed to participate, providing a sample of 3605 direct-care staff employed in 169 Swedish nursing homes. The staff assessed their managers' (n = 191) leadership behaviours using the Leadership Behaviour Questionnaire. Data were collected from November 2013 - September 2014, and the study was completed in November 2016. A two-parameter item response theory approach and regression analyses were used to identify specific characteristics of highly rated leadership. Five specific behaviours of highly rated nursing home leadership were identified; that the manager: experiments with new ideas; controls work closely; relies on subordinates; coaches and gives direct feedback; and handles conflicts constructively. The regression analyses revealed that managers with social work backgrounds and privately run homes were significantly associated with higher leadership ratings. This study highlights the five most important leadership behaviours that characterize those nursing home managers rated highest in terms of leadership. Managers in privately run nursing homes and managers with social work backgrounds were associated with higher leadership ratings. Further work is needed to explore these behaviours and factors predictive of higher leadership ratings. © 2017 John Wiley & Sons Ltd.
Analysis of family-wise error rates in statistical parametric mapping using random field theory.
Flandin, Guillaume; Friston, Karl J
2017-11-01
This technical report revisits the analysis of family-wise error rates in statistical parametric mapping-using random field theory-reported in (Eklund et al. []: arXiv 1511.01863). Contrary to the understandable spin that these sorts of analyses attract, a review of their results suggests that they endorse the use of parametric assumptions-and random field theory-in the analysis of functional neuroimaging data. We briefly rehearse the advantages parametric analyses offer over nonparametric alternatives and then unpack the implications of (Eklund et al. []: arXiv 1511.01863) for parametric procedures. Hum Brain Mapp, 2017. © 2017 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc. © 2017 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc.
Joint Machine Learning and Game Theory for Rate Control in High Efficiency Video Coding.
Gao, Wei; Kwong, Sam; Jia, Yuheng
2017-08-25
In this paper, a joint machine learning and game theory modeling (MLGT) framework is proposed for inter frame coding tree unit (CTU) level bit allocation and rate control (RC) optimization in High Efficiency Video Coding (HEVC). First, a support vector machine (SVM) based multi-classification scheme is proposed to improve the prediction accuracy of CTU-level Rate-Distortion (R-D) model. The legacy "chicken-and-egg" dilemma in video coding is proposed to be overcome by the learning-based R-D model. Second, a mixed R-D model based cooperative bargaining game theory is proposed for bit allocation optimization, where the convexity of the mixed R-D model based utility function is proved, and Nash bargaining solution (NBS) is achieved by the proposed iterative solution search method. The minimum utility is adjusted by the reference coding distortion and frame-level Quantization parameter (QP) change. Lastly, intra frame QP and inter frame adaptive bit ratios are adjusted to make inter frames have more bit resources to maintain smooth quality and bit consumption in the bargaining game optimization. Experimental results demonstrate that the proposed MLGT based RC method can achieve much better R-D performances, quality smoothness, bit rate accuracy, buffer control results and subjective visual quality than the other state-of-the-art one-pass RC methods, and the achieved R-D performances are very close to the performance limits from the FixedQP method.
Berezhkovskii, Alexander M.; Frishman, Anatoli M.; Pollak, Eli
1994-09-01
Variational transition state theory (VTST) is applied to the study of the activated escape of a particle trapped in a multidimensional potential well and coupled to a heat bath. Special attention is given to the dependence of the rate constant on the friction coefficients in the case of anisotropic friction. It is demonstrated explicitly that both the traditional as well as the nontraditional scenarios for the particle escape are recovered uniformly within the framework of VTST. Effects such as saddle point avoidance and friction dependence of the activation energy are derived from VTST using optimized planar dividing surfaces.
Absence of saturation of void growth in rate theory with anisotropic diffusion
Hudson, T S; Sutton, A P
2002-01-01
We present a first attempt at solution the problem of the growth of a single void in the presence of anisotropically diffusing radiation induced self-interstitial atom (SIA) clusters. In order to treat a distribution of voids we perform ensemble averaging over the positions of centres of voids using a mean-field approximation. In this way we are able to model physical situations in between the Standard Rate Theory (SRT) treatment of swelling (isotropic diffusion), and the purely 1-dimensional diffusion of clusters in the Production Bias Model. The background absorption by dislocations is however treated isotropically, with a bias for interstitial cluster absorption assumed similar to that of individual SIAs. We find that for moderate anisotropy, unsaturated void growth is characteristic of this anisotropic diffusion of clusters. In addition we obtain a higher initial void swelling rate than predicted by SRT whenever the diffusion is anisotropic.
Beta-decay rate and beta-delayed neutron emission probability of improved gross theory
Koura, Hiroyuki
2014-09-01
A theoretical study has been carried out on beta-decay rate and beta-delayed neutron emission probability. The gross theory of the beta decay is based on an idea of the sum rule of the beta-decay strength function, and has succeeded in describing beta-decay half-lives of nuclei overall nuclear mass region. The gross theory includes not only the allowed transition as the Fermi and the Gamow-Teller, but also the first-forbidden transition. In this work, some improvements are introduced as the nuclear shell correction on nuclear level densities and the nuclear deformation for nuclear strength functions, those effects were not included in the original gross theory. The shell energy and the nuclear deformation for unmeasured nuclei are adopted from the KTUY nuclear mass formula, which is based on the spherical-basis method. Considering the properties of the integrated Fermi function, we can roughly categorized energy region of excited-state of a daughter nucleus into three regions: a highly-excited energy region, which fully affect a delayed neutron probability, a middle energy region, which is estimated to contribute the decay heat, and a region neighboring the ground-state, which determines the beta-decay rate. Some results will be given in the presentation. A theoretical study has been carried out on beta-decay rate and beta-delayed neutron emission probability. The gross theory of the beta decay is based on an idea of the sum rule of the beta-decay strength function, and has succeeded in describing beta-decay half-lives of nuclei overall nuclear mass region. The gross theory includes not only the allowed transition as the Fermi and the Gamow-Teller, but also the first-forbidden transition. In this work, some improvements are introduced as the nuclear shell correction on nuclear level densities and the nuclear deformation for nuclear strength functions, those effects were not included in the original gross theory. The shell energy and the nuclear deformation for
Energy Technology Data Exchange (ETDEWEB)
Greene, Samuel M., E-mail: samuel.greene@chem.ox.ac.uk; Shan, Xiao, E-mail: xiao.shan@chem.ox.ac.uk; Clary, David C., E-mail: david.clary@chem.ox.ac.u [Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)
2016-06-28
Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.
Generalized Rate Theory for Void and Bubble Swelling and its Application to Delta-Plutonium
Energy Technology Data Exchange (ETDEWEB)
Allen, P. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Wall, M. A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Wolfer, W. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
2016-10-04
A rate theory for void and bubble swelling is derived that allows both vacancies and self-interstitial atoms to be generated by thermal activation at all sinks. In addition, they can also be produced by displacement damage from external and internal radiation. This generalized rate theory (GRT) is applied to swelling of gallium-stabilized δ-plutonium in which α-decay causes the displacement damage. Since the helium atoms produced also become trapped in vacancies, a distinction is made between empty and occupied vacancies. The growth of helium bubbles observed by transmission electron microscopy (TEM) in weapons-grade and in material enriched with Pu238 is analyzed, using different values for the formation energy of self-interstitial atoms (SIA) and two different sets of relaxation volumes for the vacancy and for the SIA. One set allows preferential capture of SIA at dislocations, while the other set gives equal preference to both vacancy and SIA. It is found that the helium bubble diameters observed are in better agreement with GRT predictions if no preferential capture occurs at dislocations. Therefore, helium bubbles in δ-plutonium will not evolve into voids. The helium density within the bubbles remains sufficiently high to cause thermal emission of SIA. Based on a helium density between two to three helium atoms per vacant site, the sum of formation and migration energies must be around 2.0 eV for SIA in δ-plutonium.
Crossover behavior of the thermal conductance and Kramers’ transition rate theory
Velizhanin, Kirill A.; Sahu, Subin; Chien, Chih-Chun; Dubi, Yonatan; Zwolak, Michael
2015-12-01
Kramers’ theory frames chemical reaction rates in solution as reactants overcoming a barrier in the presence of friction and noise. For weak coupling to the solution, the reaction rate is limited by the rate at which the solution can restore equilibrium after a subset of reactants have surmounted the barrier to become products. For strong coupling, there are always sufficiently energetic reactants. However, the solution returns many of the intermediate states back to the reactants before the product fully forms. Here, we demonstrate that the thermal conductance displays an analogous physical response to the friction and noise that drive the heat current through a material or structure. A crossover behavior emerges where the thermal reservoirs dominate the conductance at the extremes and only in the intermediate region are the intrinsic properties of the lattice manifest. Not only does this shed new light on Kramers’ classic turnover problem, this result is significant for the design of devices for thermal management and other applications, as well as the proper simulation of transport at the nanoscale.
Proeschold-Bell, Rae Jean; Miles, Andrew; Toth, Matthew; Adams, Christopher; Smith, Bruce W; Toole, David
2013-12-01
The clergy occupation is unique in its combination of role strains and higher calling, putting clergy mental health at risk. We surveyed all United Methodist clergy in North Carolina, and 95% (n = 1,726) responded, with 38% responding via phone interview. We compared clergy phone interview depression rates, assessed using the Patient Health Questionnaire (PHQ-9), to those of in-person interviews in a representative United States sample that also used the PHQ-9. The clergy depression prevalence was 8.7%, significantly higher than the 5.5% rate of the national sample. We used logistic regression to explain depression, and also anxiety, assessed using the Hospital Anxiety and Depression Scale. As hypothesized by effort-reward imbalance theory, several extrinsic demands (job stress, life unpredictability) and intrinsic demands (guilt about not doing enough work, doubting one's call to ministry) significantly predicted depression and anxiety, as did rewards such as ministry satisfaction and lack of financial stress. The high rate of clergy depression signals the need for preventive policies and programs for clergy. The extrinsic and intrinsic demands and rewards suggest specific actions to improve clergy mental health.
A permutation information theory tour through different interest rate maturities: the Libor case.
Bariviera, Aurelio Fernández; Guercio, María Belén; Martinez, Lisana B; Rosso, Osvaldo A
2015-12-13
This paper analyses Libor interest rates for seven different maturities and referred to operations in British pounds, euros, Swiss francs and Japanese yen, during the period 2001-2015. The analysis is performed by means of two quantifiers derived from information theory: the permutation Shannon entropy and the permutation Fisher information measure. An anomalous behaviour in the Libor is detected in all currencies except euros during the years 2006-2012. The stochastic switch is more severe in one, two and three months maturities. Given the special mechanism of Libor setting, we conjecture that the behaviour could have been produced by the manipulation that was uncovered by financial authorities. We argue that our methodology is pertinent as a market overseeing instrument. © 2015 The Author(s).
Energy Technology Data Exchange (ETDEWEB)
Jain, Amber; Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104 (United States)
2015-10-07
We investigate a simple approach to compute a non-adiabatic thermal rate constant using the fewest switches surface hopping (FSSH) dynamics. We study the effects of both decoherence (using our augmented-FSSH (A-FSSH) algorithm) and forbidden hops over a large range of parameters, including high and low friction regimes, and weak and strong electronic coupling regimes. Furthermore, when possible, we benchmark our results against exact hierarchy equations of motion results, where we usually find a maximum error of roughly a factor of two (at reasonably large temperatures). In agreement with Hammes-Schiffer and Tully, we find that a merger of transition state theory and surface hopping can be both accurate and efficient when performed correctly. We further show that detailed balance is followed approximately by A-FSSH dynamics.
International Nuclear Information System (INIS)
Jambon, C.
1962-01-01
After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [fr
Rate Theory Modeling and Simulations of Silicide Fuel at LWR Conditions
Energy Technology Data Exchange (ETDEWEB)
Miao, Yinbin [Argonne National Lab. (ANL), Argonne, IL (United States); Ye, Bei [Argonne National Lab. (ANL), Argonne, IL (United States); Mei, Zhigang [Argonne National Lab. (ANL), Argonne, IL (United States); Hofman, Gerard [Argonne National Lab. (ANL), Argonne, IL (United States); Yacout, Abdellatif [Argonne National Lab. (ANL), Argonne, IL (United States)
2015-12-10
Uranium silicide (U_{3}Si_{2}) fuel has higher thermal conductivity and higher uranium density, making it a promising candidate for the accident-tolerant fuel (ATF) used in light water reactors (LWRs). However, previous studies on the fuel performance of U_{3}Si_{2}, including both experimental and computational approaches, have been focusing on the irradiation conditions in research reactors, which usually involve low operation temperatures and high fuel burnups. Thus, it is important to examine the fuel performance of U_{3}Si_{2} at typical LWR conditions so as to evaluate the feasibility of replacing conventional uranium dioxide fuel with this silicide fuel material. As in-reactor irradiation experiments involve significant time and financial cost, it is appropriate to utilize modeling tools to estimate the behavior of U_{3}Si_{2} in LWRs based on all those available research reactor experimental references and state-of-the-art density functional theory (DFT) calculation capabilities at the early development stage. Hence, in this report, a comprehensive investigation of the fission gas swelling behavior of U_{3}Si_{2} at LWR conditions is introduced. The modeling efforts mentioned in this report was based on the rate theory (RT) model of fission gas bubble evolution that has been successfully applied for a variety of fuel materials at devious reactor conditions. Both existing experimental data and DFT-calculated results were used for the optimization of the parameters adopted by the RT model. Meanwhile, the fuel-cladding interaction was captured by the coupling of the RT model with simplified mechanical correlations. Therefore, the swelling behavior of U_{3}Si_{2} fuel and its consequent interaction with cladding in LWRs was predicted by the rate theory modeling, providing valuable information for the development of U_{3}Si_{2} fuel as an accident
Larkin, Allie C; Nestler, Matthew J; Smith, Caleb A; Heard, George L; Setser, Donald W; Holmes, Bert E
2016-10-03
Chemically activated C2D5CHCl2 molecules were generated with 88 kcal mol-1 of vibrational energy by the recombination of C2D5 and CHCl2 radicals in a room temperature bath gas. The competing 2,1-DCl and 1,1-HCl unimolecular reactions were identified by the observation of the CD3CD=CHCl and CD3CD=CDCl products. The initial CD3CD2C-Cl carbene product from 1,1-HCl elimination rearranges to CD3CD=CDCl under the conditions of the experiments. The experimental rate constants were 2.7 x107 and 0.47 x107 s-1 for 2,1-DCl and 1,1-HCl elimination reactions, respectively, which corresponds to branching fractions of 0.84 and 0.16. The experimental rate constants were compared to calculated statistical rate constants to assign threshold energies of 54 and ≈ 66 kcal mol-1 for the 1,2-DCl and 1,1-HCl reactions, respectively. The statistical rate constants were obtained from models developed from electronic-structure calculations for the molecule and its transition states. The rate constant (5.3 x 107 s-1) for the unimolecular decomposition of CHCl2CHCl2 molecules formed with 82 kcal mol-1 of vibrational energy by the recombination of CHCl2 radicals also is reported. Based upon the magnitude of the calculated rate constant, 1,1-HCl elimination must contribute less than 15% to the reaction; 1,2-HCl elimination is the major reaction and the threshold energy is 59 kcal mol-1. Calculations also were done to analyze previously published rate constants for chemically activated CD2Cl-CHCl2 molecules with 86 kcal mol-1 of energy in order to obtain a better overall description of the nature of the 1,1-HCl pathway for 1,1-dichloroalkanes. The interplay of the threshold energies for the 2,1-HCl and 1,1-HCl reactions and the available energy determines the product branching fractions for individual molecules. The unusual nature of the transition state for 1,1-HCl elimination is discussed.
Evaporation of Liquid Droplet in Nano and Micro Scales from Statistical Rate Theory.
Duan, Fei; He, Bin; Wei, Tao
2015-04-01
The statistical rate theory (SRT) is applied to predict the average evaporation flux of liquid droplet after the approach is validated in the sessile droplet experiments of the water and heavy water. The steady-state experiments show a temperature discontinuity at the evaporating interface. The average evaporation flux is evaluated by individually changing the measurement at a liquid-vapor interface, including the interfacial liquid temperature, the interfacial vapor temperature, the vapor-phase pressure, and the droplet size. The parameter study shows that a higher temperature jump would reduce the average evaporation flux. The average evaporation flux can significantly be influenced by the interfacial liquid temperature and the vapor-phase pressure. The variation can switch the evaporation into condensation. The evaporation flux is found to remain relative constant if the droplet is larger than a micro scale, while the smaller diameters in nano scale can produce a much higher evaporation flux. In addition, a smaller diameter of droplets with the same liquid volume has a larger surface area. It is suggested that the evaporation rate increases dramatically as the droplet shrinks into nano size.
Bao, Junwei Lucas; Zheng, Jingjing; Truhlar, Donald G
2016-03-02
Pressure-dependent reactions are ubiquitous in combustion and atmospheric chemistry. We employ a new calibration procedure for quantum Rice-Ramsperger-Kassel (QRRK) unimolecular rate theory within a chemical activation mechanism to calculate the pressure-falloff effect of a radical association with an aromatic ring. The new theoretical framework is applied to the reaction of H with toluene, which is a prototypical reaction in the combustion chemistry of aromatic hydrocarbons present in most fuels. Both the hydrogen abstraction reactions and the hydrogen addition reactions are calculated. Our system-specific (SS) QRRK approach is adjusted with SS parameters to agree with multistructural canonical variational transition state theory with multidimensional tunneling (MS-CVT/SCT) at the high-pressure limit. The new method avoids the need for the usual empirical estimations of the QRRK parameters, and it eliminates the need for variational transition state theory calculations as a function of energy, although in this first application we do validate the falloff curves by comparing SS-QRRK results without tunneling to multistructural microcanonical variational transition state theory (MS-μVT) rate constants without tunneling. At low temperatures, the two approaches agree well with each other, but at high temperatures, SS-QRRK tends to overestimate falloff slightly. We also show that the variational effect is important in computing the energy-resolved rate constants. Multiple-structure anharmonicity, torsional-potential anharmonicity, and high-frequency-mode vibrational anharmonicity are all included in the rate computations, and torsional anharmonicity effects on the density of states are investigated. Branching fractions, which are both temperature- and pressure-dependent (and for which only limited data is available from experiment), are predicted as a function of pressure.
Liechty, Derek S.; Lewis, Mark J.
2010-01-01
Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.
Using NIF to Test Theories of High-Pressure, High-Rate Plastic Flow in Metals
Rudd, Robert E.; Arsenlis, A.; Cavallo, R. M.; Huntington, C. M.; McNaney, J. M.; Park, H. S.; Powell, P.; Prisbrey, S. T.; Remington, B. A.; Swift, D.; Wehrenberg, C. E.; Yang, L.
2017-10-01
Precisely controlled plasmas are playing key roles both as pump and probe in experiments to understand the strength of solid metals at high energy density (HED) conditions. In concert with theoretical advances, these experiments have enabled a predictive capability to model material strength at Mbar pressures and high strain rates. Here we describe multiscale strength models developed for tantalum starting with atomic bonding and extending up through the mobility of individual dislocations, the evolution of dislocation networks and so on until the ultimate material response at the scale of an experiment. Experiments at the National Ignition Facility (NIF) probe strength in metals ramp compressed to 1-8 Mbar. The model is able to predict 1 Mbar experiments without adjustable parameters. The combination of experiment and theory has shown that solid metals can behave significantly differently at HED conditions. We also describe recent studies of lead compressed to 3-5 Mbar. Work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE-AC52-07NA273.
Rolland, Jonathan; Loiseau, Oriane; Romiguier, Jonathan; Salamin, Nicolas
2016-05-20
The metabolic theory of ecology stipulates that molecular evolutionary rates should correlate with temperature and latitude in ectothermic organisms. Previous studies have shown that most groups of vertebrates, such as amphibians, turtles and even endothermic mammals, have higher molecular evolutionary rates in regions where temperature is high. However, the association between molecular evolutionary rates and temperature or latitude has never been tested in Squamata. We used a large dataset including the spatial distributions and environmental variables for 1,651 species of Squamata and compared the contrast of the rates of molecular evolution with the contrast of temperature and latitude between sister species. Using major axis regressions and a new algorithm to choose independent sister species pairs, we found that temperature and absolute latitude were not associated with molecular evolutionary rates. This absence of association in such a diverse ectothermic group questions the mechanisms explaining current pattern of species diversity in Squamata and challenges the presupposed universality of the metabolic theory of ecology.
Behnaz Shahrokh; Garnik N. Sargsyan; Arkadi B. Harutyunyan
2012-01-01
Investigations of the unimolecular decomposition of vinyl ethyl ether (VEE), vinyl propyl ether (VPE) and vinyl butyl ether (VBE) have shown that activation of the molecule of a ether results in formation of a cyclic construction - the transition state (TS), which may lead to the displacement of the thermodynamic equilibrium towards the reaction products. The TS is obtained by applying energy minimization relative to the ground state of an ether under the program MM2 when...
International Nuclear Information System (INIS)
Lee, Gyeong Geun; Lee, Yong Bok; Kim, Min Chul; Kwon, Junh Yun
2012-01-01
Neutron irradiation to reactor pressure vessel (RPV) steels causes a decrease in fracture toughness and an increase in yield strength while in service. It is generally accepted that the growth of point defect cluster (PDC) and copper rich precipitate (CRP) affects radiation hardening of RPV steels. A number of models have been proposed to account for the embrittlement of RPV steels. The rate theory based modeling mathematically described the evolution of radiation induced microstructures of ferritic steels under neutron irradiation. In this work, we compared the rate theory based modeling calculation with the surveillance test results of Korean Light Water Reactors (LWRs)
Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.
Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua
2016-03-03
The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.
Directory of Open Access Journals (Sweden)
M. J. Newland
2018-05-01
CHOO. The experimental results are interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H2O, characterised for α-pinene and β-pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that > 97 % of the total monoterpene-derived global SCI burden is comprised of SCIs with a structure that determines that they react slowly with water and that their atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCIs reach up to 1.4 × 104 cm−3 in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene-derived SCIs with SO2 account for < 1 % globally but may account for up to 60 % of the gas-phase SO2 removal over areas of tropical forests, with significant localised impacts on the formation of sulfate aerosol and hence the lifetime and distribution of SO2.
Newland, Mike J.; Rickard, Andrew R.; Sherwen, Tomás; Evans, Mathew J.; Vereecken, Luc; Muñoz, Amalia; Ródenas, Milagros; Bloss, William J.
2018-05-01
interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H2O, characterised for α-pinene and β-pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that > 97 % of the total monoterpene-derived global SCI burden is comprised of SCIs with a structure that determines that they react slowly with water and that their atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCIs reach up to 1.4 × 104 cm-3 in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene-derived SCIs with SO2 account for < 1 % globally but may account for up to 60 % of the gas-phase SO2 removal over areas of tropical forests, with significant localised impacts on the formation of sulfate aerosol and hence the lifetime and distribution of SO2.
Rate theory scenarios study on fission gas behavior of U 3 Si 2 under LOCA conditions in LWRs
Energy Technology Data Exchange (ETDEWEB)
Miao, Yinbin; Gamble, Kyle A.; Andersson, David; Mei, Zhi-Gang; Yacout, Abdellatif M.
2018-01-01
Fission gas behavior of U3Si2 under various loss-of-coolant accident (LOCA) conditions in light water reactors (LWRs) was simulated using rate theory. A rate theory model for U3Si2 that covers both steady-state operation and power transients was developed for the GRASS-SST code based on existing research reactor/ion irradiation experimental data and theoretical predictions of density functional theory (DFT) calculations. The steady-state and LOCA condition parameters were either directly provided or inspired by BISON simulations. Due to the absence of in-pile experiment data for U3Si2's fuel performance under LWR conditions at this stage of accident tolerant fuel (ATF) development, a variety of LOCA scenarios were taken into consideration to comprehensively and conservatively evaluate the fission gas behavior of U3Si2 during a LOCA.
Gray, Kishonna L.
2012-01-01
This article examines the response of minority gamers as they adopt new innovations in Xbox Live. Using diffusion of innovation theory, specific attention is given to gamers' rate of adoption of the new Xbox Live environment, which was a recent update to the Xbox Live interface. By employing virtual ethnography, observations, and interviews reveal…
International Nuclear Information System (INIS)
Danen, W.C.
1979-01-01
It has been demonstrated that a mixture of reactant molecules can be induced by pulsed infrared laser radiation to react via a route which is totally different from the pathway resulting from heating the mixture at 300 0 C. The high-energy unimolecular elimination of H 2 O from ethanol in the presence of 2-propanol and HBr can be selectively induced with a pulsed CO 2 laser in preference to either a lower energy bimolecular HBr-catalyzed dehydration or the more facile dehydration of 2-propanol. Heating the mixture resulted in the almost exclusive reaction of 2-propanol to produce propylene. It was demonstrated that the bimolecular ethanol + HBr reaction cannot be effectively induced by the infrared laser radiation as evidenced by the detrimental effect on the yield of ethylene as the HBr pressure was increased. The selective, nonthermal inducement of H 2 O elimination from vibrationally excited ethanol in the presence of 2-propanol required relatively low reactant pressures. At higher pressures intermolecular V--V energy transfer allowed the thermally more facile dehydration from 2-propanol to become the predominant reaction channel
Proton transfer and unimolecular decay in the low-energy-reaction dynamics of H3O+ with acetone
International Nuclear Information System (INIS)
Creasy, W.R.; Farrar, J.M.
1983-01-01
The title reaction has been studied at collision energies of 0.83 and 2.41 eV. Direct reaction dynamics have been observed at both energies and an increasingly high fraction of the total energy appears in product translation as the collision energy increases. This result is consistent with the concept of induced repulsive energy release, which becomes more effective as trajectories sample the corner of the potential energy surface. At the higher collision energy, the protonated acetone cation undergoes two unimolecular decay channels: C-C bond cleavage to CH 3 CO + and CH 4 , and C-O bond cleavagto C 3 H 5 + (presumably to allyl cation) and H 2 O. The CH 3 CO + channel, endothermic relative to ground state protonated acetone cations by 0.74 eV, appears to liberate 0.4 eV in relative product translation while the C 3 H 5 + channel, endothermic by 2.17 eV, liberates only 0.07 eV in relative translation. These results are discussed in terms of the location on the reaction coordinate and magnitudes of potential energy barriers to 1,3-hydrogen atoms shifts which must precede the bond cleavage processes
Hao, Tian
2017-02-22
The Hall effects, especially the integer, fractional and anomalous quantum Hall effects, have been addressed using Eyring's rate process theory and free volume concept. The basic assumptions are that the conduction process is a common rate controlled "reaction" process that can be described with Eyring's absolute rate process theory; the mobility of electrons should be dependent on the free volume available for conduction electrons. The obtained Hall conductivity is clearly quantized as with prefactors related to both the magnetic flux quantum number and the magnetic quantum number via the azimuthal quantum number, with and without an externally applied magnetic field. This article focuses on two dimensional (2D) systems, but the approaches developed in this article can be extended to 3D systems.
Rate theory of solvent exchange and kinetics of Li(+) - BF4 (-)/PF6 (-) ion pairs in acetonitrile.
Dang, Liem X; Chang, Tsun-Mei
2016-09-07
In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li(+) and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li(+) in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li(+)-[BF4] and Li(+)-[PF6] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li(+). We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li(+)-[BF4] and Li(+)-[PF6] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.
Zietsch, Brendan P; Miller, Geoffrey F; Bailey, J Michael; Martin, Nicholas G
2011-08-01
The criteria for "female orgasmic disorder" (FOD) assume that low rates of orgasm are dysfunctional, implying that high rates are functional. Evolutionary theories about the function of female orgasm predict correlations of orgasm rates with sexual attitudes and behavior and other fitness-related traits. To test hypothesized evolutionary functions of the female orgasm. We examined such correlations in a community sample of 2,914 adult female Australian twins who reported their orgasm rates during masturbation, intercourse, and other sexual activities, and who completed demographic, personality, and sexuality questionnaires. Orgasm rates during intercourse, other sex, and masturbation. Although orgasm rates showed high variance across women and substantial heritability, they were largely phenotypically and genetically independent of other important traits. We found zero to weak phenotypic correlations between all three orgasm rates and all other 19 traits examined, including occupational status, social class, educational attainment, extraversion, neuroticism, psychoticism, impulsiveness, childhood illness, maternal pregnancy stress, marital status, political liberalism, restrictive attitudes toward sex, libido, lifetime number of sex partners, risky sexual behavior, masculinity, orientation toward uncommitted sex, age of first intercourse, and sexual fantasy. Furthermore, none of the correlations had significant genetic components. These findings cast doubt on most current evolutionary theories about female orgasm's adaptive functions, and on the validity of FOD as a psychiatric construct. © 2011 International Society for Sexual Medicine.
Chimpanzee choice rates in competitive games match equilibrium game theory predictions.
Martin, Christopher Flynn; Bhui, Rahul; Bossaerts, Peter; Matsuzawa, Tetsuro; Camerer, Colin
2014-06-05
The capacity for strategic thinking about the payoff-relevant actions of conspecifics is not well understood across species. We use game theory to make predictions about choices and temporal dynamics in three abstract competitive situations with chimpanzee participants. Frequencies of chimpanzee choices are extremely close to equilibrium (accurate-guessing) predictions, and shift as payoffs change, just as equilibrium theory predicts. The chimpanzee choices are also closer to the equilibrium prediction, and more responsive to past history and payoff changes, than two samples of human choices from experiments in which humans were also initially uninformed about opponent payoffs and could not communicate verbally. The results are consistent with a tentative interpretation of game theory as explaining evolved behavior, with the additional hypothesis that chimpanzees may retain or practice a specialized capacity to adjust strategy choice during competition to perform at least as well as, or better than, humans have.
Gulvi, Nitin R.; Patel, Priyanka; Badani, Purav M.
2018-04-01
Pathway for dissociation of multihalogenated alkyls is observed to be competitive between molecular and atomic elimination products. Factors such as molecular structure, temperature and pressure are known to influence the same. Hence present work is focussed to explore mechanism and kinetics of atomic (Br) and molecular (HBr and Br2) elimination upon pyrolysis of 1,1- and 1,2-ethyl dibromide (EDB). For this purpose, electronic structure calculations were performed at DFT and CCSD(T) level of theory. In addition to concerted mechanism, an alternate energetically efficient isomerisation pathway has been exploited for molecular elimination. Energy calculations are further complimented by detailed kinetic investigation, over wide range of temperature and pressure, using suitable models like Canonical Transition State Theory, Statistical Adiabatic Channel Model and Troe's formalism. Our calculations suggest high branching ratio for dehydrohalogentation reaction, from both isomers of EDB. Fall off curve depicts good agreement between theoretically estimated and experimentally reported values.
Gallis, Michael A; Bond, Ryan B; Torczynski, John R
2009-09-28
Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.
Social Disorganization Theory and Crime Rates on California Community College Campuses
Ravalin, Tamara; Tevis, Tenisha
2017-01-01
Recent media attention concerning the escalation of crime on college campuses has created a sense of urgency to address how crime will impact the largest community college system in the United States, California Community Colleges. Crime can deter academic success and social engagement. This study utilizes social disorganization theory to examine…
Czech Academy of Sciences Publication Activity Database
Adam, Jiří; Tater, Miloš; Truhlík, Emil; Epelbaum, E.; Machleidt, R.; Ricci, P.
2012-01-01
Roč. 709, 1-2 (2012), s. 93-100 ISSN 0370-2693 R&D Projects: GA MŠk LC06002; GA ČR GAP203/11/0701 Institutional support: RVO:61389005 Keywords : negative muon capture * deuteron * effective field theory * meson exchange currents Subject RIV: BE - Theoretical Physics Impact factor: 4.569, year: 2012
McDowell, J. J; Wood, Helena M.
1985-01-01
Four human subjects worked on all combinations of five variable-interval schedules and five reinforcer magnitudes (¢/reinforcer) in each of two phases of the experiment. In one phase the force requirement on the operandum was low (1 or 11 N) and in the other it was high (25 or 146 N). Estimates of Herrnstein's κ were obtained at each reinforcer magnitude. The results were: (1) response rate was more sensitive to changes in reinforcement rate at the high than at the low force requirement, (2) κ increased from the beginning to the end of the magnitude range for all subjects at both force requirements, (3) the reciprocal of κ was a linear function of the reciprocal of reinforcer magnitude for seven of the eight data sets, and (4) the rate of change of κ was greater at the high than at the low force requirement by an order of magnitude or more. The second and third findings confirm predictions made by linear system theory, and replicate the results of an earlier experiment (McDowell & Wood, 1984). The fourth finding confirms a further prediction of the theory and supports the theory's interpretation of conflicting data on the constancy of Herrnstein's κ. PMID:16812408
McDowell, J J; Wood, H M
1985-01-01
Four human subjects worked on all combinations of five variable-interval schedules and five reinforcer magnitudes ( cent/reinforcer) in each of two phases of the experiment. In one phase the force requirement on the operandum was low (1 or 11 N) and in the other it was high (25 or 146 N). Estimates of Herrnstein's kappa were obtained at each reinforcer magnitude. The results were: (1) response rate was more sensitive to changes in reinforcement rate at the high than at the low force requirement, (2) kappa increased from the beginning to the end of the magnitude range for all subjects at both force requirements, (3) the reciprocal of kappa was a linear function of the reciprocal of reinforcer magnitude for seven of the eight data sets, and (4) the rate of change of kappa was greater at the high than at the low force requirement by an order of magnitude or more. The second and third findings confirm predictions made by linear system theory, and replicate the results of an earlier experiment (McDowell & Wood, 1984). The fourth finding confirms a further prediction of the theory and supports the theory's interpretation of conflicting data on the constancy of Herrnstein's kappa.
Computing decay rates for new physics theories with FEYNRULES and MADGRAPH 5_AMC@NLO
Alwall, Johan; Duhr, Claude; Fuks, Benjamin; Mattelaer, Olivier; Öztürk, Deniz Gizem; Shen, Chia-Hsien
2015-12-01
We present new features of the FEYNRULES and MADGRAPH 5_AMC@NLO programs for the automatic computation of decay widths that consistently include channels of arbitrary final-state multiplicity. The implementations are generic enough so that they can be used in the framework of any quantum field theory, possibly including higher-dimensional operators. We extend at the same time the conventions of the Universal FEYNRULES Output (or UFO) format to include decay tables and information on the total widths. We finally provide a set of representative examples of the usage of the new functions of the different codes in the framework of the Standard Model, the Higgs Effective Field Theory, the Strongly Interacting Light Higgs model and the Minimal Supersymmetric Standard Model and compare the results to available literature and programs for validation purposes.
Communication about future policy rates in theory and practice : a survey
Moessner, R.; Jansen, David-Jan; de Haan, Jakob
We discuss the theoretical rationale for central bank communication about future policy rates, either as part of inflation targeting or in the form of forward guidance. We also summarize both actual central bank communication about future policy rates and empirical evidence on the effectiveness of
Directory of Open Access Journals (Sweden)
Oreiro José Luis
2013-01-01
Full Text Available This article analyzes the relationship between economic growth, income distribution and real exchange rate within the neo-Kaleckian literature, through the construction of a nonlinear macrodynamic model for an open economy in which investment in fixed capital is assumed to be a quadratic function of the real exchange rate. The model demonstrates that the prevailing regime of accumulation in a given economy depends on the type of currency misalignment, so if the real exchange rate is overvalued, then the regime of accumulation will be profit-led, but if the exchange rate is undervalued, then the accumulation regime is wage-led. Subsequently, the adherence of the theoretical model to data is tested for Brazil in the period 1994/Q3-2008/Q4. The econometric results are consistent with the theoretical non-linear specification of the investment function used in the model, so that we can define the existence of a real exchange rate that maximizes the rate of capital accumulation for the Brazilian economy. From the estimate of this optimal rate we show that the real exchange rate is overvalued in 1994/Q3- 2001/Q1 and 2005/Q4-2008/Q4 and undervalued in the period 2001/Q2-2005/Q3. As a direct corollary of this result, it follows that the prevailing regime of accumulation in the Brazilian economy after the last quarter of 2005 is profit-led.
Reaction-rate formula in out of equilibrium quantum field theory
Niegawa, A.; Okano, K.; Ozaki, H.
1999-01-01
A complete derivation, from first principles, of the reaction-rate formula for a generic reaction taking place in an out of equilibrium quantum-field system is given. It is shown that the formula involves no finite-volume correction. Each term of the reaction-rate formula represents a set of physical processes that contribute to the reaction under consideration.
Should Unemployment Insurance Vary with the Unemployment Rate? Theory and Evidence
Kroft, Kory; Notowidigdo, Matthew J.
2012-01-01
We study how optimal unemployment insurance (UI) benefits vary over the business cycle by estimating how the moral hazard cost and the consumption smoothing benefit of UI vary with the unemployment rate. We find that the moral hazard cost is procyclical, greater when the unemployment rate is relatively low. By contrast, our evidence suggests that the consumption smoothing benefit of UI is acyclical. Using these estimates to calibrate our job search model, we find that a one standard deviation...
Renfree, Andrew; Martin, Louise; Micklewright, Dominic; St Clair Gibson, Alan
2014-02-01
Successful participation in competitive endurance activities requires continual regulation of muscular work rate in order to maximise physiological performance capacities, meaning that individuals must make numerous decisions with regards to the muscular work rate selected at any point in time. Decisions relating to the setting of appropriate goals and the overall strategic approach to be utilised are made prior to the commencement of an event, whereas tactical decisions are made during the event itself. This review examines current theories of decision-making in an attempt to explain the manner in which regulation of muscular work is achieved during athletic activity. We describe rational and heuristic theories, and relate these to current models of regulatory processes during self-paced exercise in an attempt to explain observations made in both laboratory and competitive environments. Additionally, we use rational and heuristic theories in an attempt to explain the influence of the presence of direct competitors on the quality of the decisions made during these activities. We hypothesise that although both rational and heuristic models can plausibly explain many observed behaviours in competitive endurance activities, the complexity of the environment in which such activities occur would imply that effective rational decision-making is unlikely. However, at present, many proposed models of the regulatory process share similarities with rational models. We suggest enhanced understanding of the decision-making process during self-paced activities is crucial in order to improve the ability to understand regulation of performance and performance outcomes during athletic activity.
Lepton asymmetry rate from quantum field theory: NLO in the hierarchical limit
Energy Technology Data Exchange (ETDEWEB)
Bödeker, D.; Sangel, M., E-mail: bodeker@physik.uni-bielefeld.de, E-mail: msangel@physik.uni-bielefeld.de [Fakultät für Physik, Universität Bielefeld, 33501 Bielefeld (Germany)
2017-06-01
The rates for generating a matter-antimatter asymmetry in extensions of the Standard Model (SM) containing right-handed neutrinos are the most interesting and least trivial co\\-efficients in the rate equations for baryogenesis through thermal leptogenesis. We obtain a relation of these rates to finite-temperature real-time correlation functions, similar to the Kubo formulas for transport coefficients. Then we consider the case of hierarchical masses for the sterile neutrinos. At leading order in their Yukawa couplings we find a simple master formula which relates the rates to a single finite temperature three-point spectral function. It is valid to all orders in g , where g denotes a SM gauge or quark Yukawa coupling. We use it to compute the rate for generating a matter-antimatter asymmetry at next-to-leading order in g in the non-relativistic regime. The corrections are of order g {sup 2}, and they amount to 4% or less.
Accurate Determination of Tunneling-Affected Rate Coefficients: Theory Assessing Experiment.
Zuo, Junxiang; Xie, Changjian; Guo, Hua; Xie, Daiqian
2017-07-20
The thermal rate coefficients of a prototypical bimolecular reaction are determined on an accurate ab initio potential energy surface (PES) using ring polymer molecular dynamics (RPMD). It is shown that quantum effects such as tunneling and zero-point energy (ZPE) are of critical importance for the HCl + OH reaction at low temperatures, while the heavier deuterium substitution renders tunneling less facile in the DCl + OH reaction. The calculated RPMD rate coefficients are in excellent agreement with experimental data for the HCl + OH reaction in the entire temperature range of 200-1000 K, confirming the accuracy of the PES. On the other hand, the RPMD rate coefficients for the DCl + OH reaction agree with some, but not all, experimental values. The self-consistency of the theoretical results thus allows a quality assessment of the experimental data.
A dual theory of price and value in a meso-scale economic model with stochastic profit rate
Greenblatt, R. E.
2014-12-01
The problem of commodity price determination in a market-based, capitalist economy has a long and contentious history. Neoclassical microeconomic theories are based typically on marginal utility assumptions, while classical macroeconomic theories tend to be value-based. In the current work, I study a simplified meso-scale model of a commodity capitalist economy. The production/exchange model is represented by a network whose nodes are firms, workers, capitalists, and markets, and whose directed edges represent physical or monetary flows. A pair of multivariate linear equations with stochastic input parameters represent physical (supply/demand) and monetary (income/expense) balance. The input parameters yield a non-degenerate profit rate distribution across firms. Labor time and price are found to be eigenvector solutions to the respective balance equations. A simple relation is derived relating the expected value of commodity price to commodity labor content. Results of Monte Carlo simulations are consistent with the stochastic price/labor content relation.
Unimolecular decomposition of formic and acetic acids: A shock tube/laser absorption study
Elwardany, A.
2014-07-16
The thermal decomposition of formic acid (HCOOH) and acetic acid (CH3COOH), two carboxylic acids which play an important role in oxygenate combustion chemistry, were investigated behind reflected shock waves using laser absorption. The rate constants of the primary decomposition pathways of these acids:(HCOOH → CO + H2 O (R 1); HCOOH → CO2 + H2 (R 2); CH3 COOH → CH4 + CO2 (R 3); CH3 COOH → CH2 CO + H2 O (R 4)) were measured using simultaneous infrared laser absorption of CO, CO2 and H2O at wavelengths of 4.56, 4.18 and 2.93 microns, respectively. Reaction test conditions covered temperatures from 1230 to 1821 K and pressures from 1.0 to 6.5 atm for dilute mixtures of acids (0.25-0.6%) in argon. The rate constants of dehydration (R1) and decarboxylation (R2) reactions of formic acid were calculated by fitting exponential functions to the measured CO, CO2 and H2O time-history profiles. These two decomposition channels were found to be in the fall-off region and have a branching ratio, k1/k2, of approximately 20 over the range of pressures studied here. The best-fit Arrhenius expressions of the first-order rates of R1 and R2 were found to be:(k1 (1 atm) = 1.03 × 1011 exp (- 25651 / T) s- 1 (± 37 %); k1 (6.5 atm) = 9.12 × 1012 exp (- 30275 / T) s- 1 (± 32 %); k2 (1 atm) = 1.79 × 108 exp (- 21133 / T) s- 1 (± 41 %); k2 (6.5 atm) = 2.73 × 108 exp (- 20074 / T) s- 1 (± 37 %)). The rate constants for acetic acid decomposition were obtained by fitting simulated profiles, using an acetic acid pyrolysis mechanism, to the measured species time-histories. The branching ratio, k4/k3, was found to be approximately 2. The decarboxylation and dehydration reactions of acetic acid appear to be in the falloff region over the tested pressure range:(k3 (1 atm) = 3.18 × 1011 exp (- 28679 / T) s- 1 (± 30 %); k3 (6 atm) = 3.51 × 1012 exp (- 31330 / T) s- 1 (± 26 %); k4 (1 atm) = 7.9 × 1011 exp (- 29056 / T) s- 1 (± 34 %); k4 (6 atm) = 6.34 × 1012 exp (- 31330 / T) s
Unimolecular decomposition of formic and acetic acids: A shock tube/laser absorption study
Elwardany, A.; Nasir, E.F.; Es-sebbar, Et-touhami; Farooq, Aamir
2014-01-01
The thermal decomposition of formic acid (HCOOH) and acetic acid (CH3COOH), two carboxylic acids which play an important role in oxygenate combustion chemistry, were investigated behind reflected shock waves using laser absorption. The rate constants of the primary decomposition pathways of these acids:(HCOOH → CO + H2 O (R 1); HCOOH → CO2 + H2 (R 2); CH3 COOH → CH4 + CO2 (R 3); CH3 COOH → CH2 CO + H2 O (R 4)) were measured using simultaneous infrared laser absorption of CO, CO2 and H2O at wavelengths of 4.56, 4.18 and 2.93 microns, respectively. Reaction test conditions covered temperatures from 1230 to 1821 K and pressures from 1.0 to 6.5 atm for dilute mixtures of acids (0.25-0.6%) in argon. The rate constants of dehydration (R1) and decarboxylation (R2) reactions of formic acid were calculated by fitting exponential functions to the measured CO, CO2 and H2O time-history profiles. These two decomposition channels were found to be in the fall-off region and have a branching ratio, k1/k2, of approximately 20 over the range of pressures studied here. The best-fit Arrhenius expressions of the first-order rates of R1 and R2 were found to be:(k1 (1 atm) = 1.03 × 1011 exp (- 25651 / T) s- 1 (± 37 %); k1 (6.5 atm) = 9.12 × 1012 exp (- 30275 / T) s- 1 (± 32 %); k2 (1 atm) = 1.79 × 108 exp (- 21133 / T) s- 1 (± 41 %); k2 (6.5 atm) = 2.73 × 108 exp (- 20074 / T) s- 1 (± 37 %)). The rate constants for acetic acid decomposition were obtained by fitting simulated profiles, using an acetic acid pyrolysis mechanism, to the measured species time-histories. The branching ratio, k4/k3, was found to be approximately 2. The decarboxylation and dehydration reactions of acetic acid appear to be in the falloff region over the tested pressure range:(k3 (1 atm) = 3.18 × 1011 exp (- 28679 / T) s- 1 (± 30 %); k3 (6 atm) = 3.51 × 1012 exp (- 31330 / T) s- 1 (± 26 %); k4 (1 atm) = 7.9 × 1011 exp (- 29056 / T) s- 1 (± 34 %); k4 (6 atm) = 6.34 × 1012 exp (- 31330 / T) s
Directory of Open Access Journals (Sweden)
Akpama Holanyo K.
2016-01-01
Full Text Available In this paper, both the bifurcation theory and the initial imperfection approach are used to predict localized necking in substrate-supported metal layers. The self-consistent scale-transition scheme is used to derive the mechanical behavior of a representative volume element of the metal layer from the behavior of its microscopic constituents (the single crystals. The mechanical behavior of the elastomer substrate follows the neo-Hookean hyperelastic model. The adherence between the two layers is assumed to be perfect. Through numerical results, it is shown that the limit strains predicted by the initial imperfection approach tend towards the bifurcation predictions when the size of the geometric imperfection in the metal layer vanishes. Also, it is shown that the addition of an elastomer layer to a metal layer enhances ductility.
Liang, L. L.; Arcus, V. L.; Heskel, M.; O'Sullivan, O. S.; Weerasinghe, L. K.; Creek, D.; Egerton, J. J. G.; Tjoelker, M. G.; Atkin, O. K.; Schipper, L. A.
2017-12-01
Temperature is a crucial factor in determining the rates of ecosystem processes such as leaf respiration (R) - the flux of plant respired carbon dioxide (CO2) from leaves to the atmosphere. Generally, respiration rate increases exponentially with temperature as modelled by the Arrhenius equation, but a recent study (Heskel et al., 2016) showed a universally convergent temperature response of R using an empirical exponential/polynomial model whereby the exponent in the Arrhenius model is replaced by a quadratic function of temperature. The exponential/polynomial model has been used elsewhere to describe shoot respiration and plant respiration. What are the principles that underlie these empirical observations? Here, we demonstrate that macromolecular rate theory (MMRT), based on transition state theory for chemical kinetics, is equivalent to the exponential/polynomial model. We re-analyse the data from Heskel et al. 2016 using MMRT to show this equivalence and thus, provide an explanation based on thermodynamics, for the convergent temperature response of R. Using statistical tools, we also show the equivalent explanatory power of MMRT when compared to the exponential/polynomial model and the superiority of both of these models over the Arrhenius function. Three meaningful parameters emerge from MMRT analysis: the temperature at which the rate of respiration is maximum (the so called optimum temperature, Topt), the temperature at which the respiration rate is most sensitive to changes in temperature (the inflection temperature, Tinf) and the overall curvature of the log(rate) versus temperature plot (the so called change in heat capacity for the system, ). The latter term originates from the change in heat capacity between an enzyme-substrate complex and an enzyme transition state complex in enzyme-catalysed metabolic reactions. From MMRT, we find the average Topt and Tinf of R are 67.0±1.2 °C and 41.4±0.7 °C across global sites. The average curvature (average
Work Adjustment Theory: An Empirical Test Using a Fuzzy Rating Scale.
Hesketh, Beryl; And Others
1992-01-01
A fuzzy graphic rating scale elicited work preferences and job perceptions of 166 (of 170) Australian bank employees. Correspondence between preferences and perceptions correlated significantly with job satisfaction. Satisfaction and performance related to tenure intentions; this relation was higher for poorer performers. (SK)
Crossing rate of labelled Poisson cluster processes and their application in the reliability theory
International Nuclear Information System (INIS)
Schrupp, K.
1986-01-01
A load process is modelled within a given interdependency system and the failure probability of a structure is estimated using the crossing rate method. The term 'labelled cluster process' is formally introduced. An approximation is given by the expected value of the point process of the crossing from the safe range to the failure range. This expected value is explicitly calculated for the instationary cluster process, the stationary borderline process, and for various types of superpositions (clustering) of such processes. (DG) [de
A SIPA-based theory of irradiation creep in the low swelling rate regime
International Nuclear Information System (INIS)
Garner, F.A.; Woo, C.H.
1991-11-01
A model is presented which describes the major facets of the relationships between irradiation creep, void swelling and applied stress. The increasing degree of anisotropy in distribution of dislocation Burger's vectors with stress level plays a major role in this model. Although bcc metals are known to creep and swell at lower rates than fcc metals, it is predicted that the creep-swelling coupling coefficient is actually larger
Directory of Open Access Journals (Sweden)
Ivan Chang
Full Text Available Mitochondrial bioenergetic processes are central to the production of cellular energy, and a decrease in the expression or activity of enzyme complexes responsible for these processes can result in energetic deficit that correlates with many metabolic diseases and aging. Unfortunately, existing computational models of mitochondrial bioenergetics either lack relevant kinetic descriptions of the enzyme complexes, or incorporate mechanisms too specific to a particular mitochondrial system and are thus incapable of capturing the heterogeneity associated with these complexes across different systems and system states. Here we introduce a new composable rate equation, the chemiosmotic rate law, that expresses the flux of a prototypical energy transduction complex as a function of: the saturation kinetics of the electron donor and acceptor substrates; the redox transfer potential between the complex and the substrates; and the steady-state thermodynamic force-to-flux relationship of the overall electro-chemical reaction. Modeling of bioenergetics with this rate law has several advantages: (1 it minimizes the use of arbitrary free parameters while featuring biochemically relevant parameters that can be obtained through progress curves of common enzyme kinetics protocols; (2 it is modular and can adapt to various enzyme complex arrangements for both in vivo and in vitro systems via transformation of its rate and equilibrium constants; (3 it provides a clear association between the sensitivity of the parameters of the individual complexes and the sensitivity of the system's steady-state. To validate our approach, we conduct in vitro measurements of ETC complex I, III, and IV activities using rat heart homogenates, and construct an estimation procedure for the parameter values directly from these measurements. In addition, we show the theoretical connections of our approach to the existing models, and compare the predictive accuracy of the rate law with
Chang, Ivan; Heiske, Margit; Letellier, Thierry; Wallace, Douglas; Baldi, Pierre
2011-01-01
Mitochondrial bioenergetic processes are central to the production of cellular energy, and a decrease in the expression or activity of enzyme complexes responsible for these processes can result in energetic deficit that correlates with many metabolic diseases and aging. Unfortunately, existing computational models of mitochondrial bioenergetics either lack relevant kinetic descriptions of the enzyme complexes, or incorporate mechanisms too specific to a particular mitochondrial system and are thus incapable of capturing the heterogeneity associated with these complexes across different systems and system states. Here we introduce a new composable rate equation, the chemiosmotic rate law, that expresses the flux of a prototypical energy transduction complex as a function of: the saturation kinetics of the electron donor and acceptor substrates; the redox transfer potential between the complex and the substrates; and the steady-state thermodynamic force-to-flux relationship of the overall electro-chemical reaction. Modeling of bioenergetics with this rate law has several advantages: (1) it minimizes the use of arbitrary free parameters while featuring biochemically relevant parameters that can be obtained through progress curves of common enzyme kinetics protocols; (2) it is modular and can adapt to various enzyme complex arrangements for both in vivo and in vitro systems via transformation of its rate and equilibrium constants; (3) it provides a clear association between the sensitivity of the parameters of the individual complexes and the sensitivity of the system's steady-state. To validate our approach, we conduct in vitro measurements of ETC complex I, III, and IV activities using rat heart homogenates, and construct an estimation procedure for the parameter values directly from these measurements. In addition, we show the theoretical connections of our approach to the existing models, and compare the predictive accuracy of the rate law with our experimentally
Tan, Jacinth J X; Kraus, Michael W
2015-03-01
The economic conditions of one's life can profoundly and systematically influence health outcomes over the life course. Our present research demonstrates that rejecting the notion that social class categories are biologically determined-a nonessentialist belief-buffers lower-class individuals from poor self-rated health and negative affect, whereas conceiving of social class categories as rooted in biology-an essentialist belief-does not. In Study 1, lower-class individuals self-reported poorer health than upper-class individuals when they endorsed essentialist beliefs but showed no such difference when they rejected such beliefs. Exposure to essentialist theories of social class also led lower-class individuals to report greater feelings of negative self-conscious emotions (Studies 2 and 3), and perceive poorer health (Study 3) than upper-class individuals, whereas exposure to nonessentialist theories did not lead to such differences. Discussion considers how lay theories of social class potentially shape long-term trajectories of health and affect of lower-class individuals. © 2015 by the Society for Personality and Social Psychology, Inc.
Rate theory of ion pairing at the water liquid-vapor interface: A case of sodium iodide
Dang, Liem X.; Schenter, Gregory K.
2018-06-01
Studies on ion pairing at interfaces have been intensified recently because of their importance in many chemical reactive phenomena, such as ion-ion interactions that are affected by interfaces and their influence on kinetic processes. In this study, we performed simulations to examine the thermodynamics and kinetics of small polarizable sodium iodide ions in the bulk and near the water liquid-vapor interface. Using classical transition state theory, we calculated the dissociation rates and corrected them with transmission coefficients obtained from the reactive flux formalism and Grote-Hynes theory. Our results show that in addition to affecting the free energy of ions in solution, the interfacial environments significantly influence the kinetics of ion pairing. The results on the relaxation time obtained using the reactive flux formalism and Grote-Hynes theory present an unequivocal picture that the interface suppresses ion dissociation. The effects of the use of molecular models on the ion interactions as well as the ion-pair configurations at the interface are also quantified and discussed.
Using game theory for perceptual tuned rate control algorithm in video coding
Luo, Jiancong; Ahmad, Ishfaq
2005-03-01
This paper proposes a game theoretical rate control technique for video compression. Using a cooperative gaming approach, which has been utilized in several branches of natural and social sciences because of its enormous potential for solving constrained optimization problems, we propose a dual-level scheme to optimize the perceptual quality while guaranteeing "fairness" in bit allocation among macroblocks. At the frame level, the algorithm allocates target bits to frames based on their coding complexity. At the macroblock level, the algorithm distributes bits to macroblocks by defining a bargaining game. Macroblocks play cooperatively to compete for shares of resources (bits) to optimize their quantization scales while considering the Human Visual System"s perceptual property. Since the whole frame is an entity perceived by viewers, macroblocks compete cooperatively under a global objective of achieving the best quality with the given bit constraint. The major advantage of the proposed approach is that the cooperative game leads to an optimal and fair bit allocation strategy based on the Nash Bargaining Solution. Another advantage is that it allows multi-objective optimization with multiple decision makers (macroblocks). The simulation results testify the algorithm"s ability to achieve accurate bit rate with good perceptual quality, and to maintain a stable buffer level.
Energy Technology Data Exchange (ETDEWEB)
Sissay, Adonay [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J. [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Lopata, Kenneth, E-mail: klopata@lsu.edu [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States)
2016-09-07
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
International Nuclear Information System (INIS)
Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J.; Lopata, Kenneth
2016-01-01
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
Pham, Tien Hung; Rühaak, Wolfram; Sass, Ingo
2017-04-01
Extensive groundwater extraction leads to a drawdown of the ground water table. Consequently, soil effective stress increases and can cause land subsidence. Analysis of land subsidence generally requires a numerical model based on poroelasticity theory, which was first proposed by Biot (1941). In the review of regional land subsidence accompanying groundwater extraction, Galloway and Burbey (2011) stated that more research and application is needed in coupling of stress-dependent land subsidence process. In geotechnical field, the constant rate of strain tests (CRS) was first introduced in 1969 (Smith and Wahls 1969) and was standardized in 1982 through the designation D4186-82 by American Society for Testing and Materials. From the reading values of CRS tests, the stress-dependent parameters of poroelasticity model can be calculated. So far, there is no research to link poroelasticity theory with CRS tests in modelling land subsidence due to groundwater extraction. One dimensional CRS tests using conventional compression cell and three dimension CRS tests using Rowe cell were performed. The tests were also modelled by using finite element method with mixed elements. Back analysis technique is used to find the suitable values of hydraulic conductivity and bulk modulus that depend on the stress or void ratio. Finally, the obtained results are used in land subsidence models. Biot, M. A. (1941). "General theory of three-dimensional consolidation." Journal of applied physics 12(2): 155-164. Galloway, D. L. and T. J. Burbey (2011). "Review: Regional land subsidence accompanying groundwater extraction." Hydrogeology Journal 19(8): 1459-1486. Smith, R. E. and H. E. Wahls (1969). "Consolidation under constant rates of strain." Journal of Soil Mechanics & Foundations Div.
Lockwood, M.; Smith, M. F.
1994-01-01
We present predictions of the signatures of magnetosheath particle precipitation (in the regions classified as open low-latitude boundary layer, cusp, mantle and polar cap) for periods when the interplanetary magnetic field has a southward component. These are made using the 'pulsating cusp' model of the effects of time-varying magnetic reconnection at the dayside magnetopause. Predictions are made for both low-altitude satellites in the topside ionosphere and for midaltitude spacecraft in the magnetosphere. Low-altitude cusp signatures, which show a continuous ion dispersion signature, reveal 'quasi-steady reconnection' (one limit of the pulsating cusp model), which persists for a period of at least 10 min. We estimate that 'quasi-steady' in this context corresponds to fluctuations in the reconnection rate of a factor of 2 or less. The other limit of the pulsating cusp model explains the instantaneous jumps in the precipitating ion spectrum that have been observed at low altitudes. Such jumps are produced by isolated pulses of reconnection: that is, they are separated by intervals when the reconnection rate is zero. These also generate convecting patches on the magnetopause in which the field lines thread the boundary via a rotational discontinuity separated by more extensive regions of tangential discontinuity. Predictions of the corresponding ion precipitation signatures seen by midaltitude spacecraft are presented. We resolve the apparent contradiction between estimates of the width of the injection region from midaltitude data and the concept of continuous entry of solar wind plasma along open field lines. In addition, we reevaluate the use of pitch angle-energy dispersion to estimate the injection distance.
Mazyar, Oleg A.; Mayer, Paul M.; Baer, Tomas
1997-11-01
Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy has been used to investigate the unimolecular chemistry of metastable methyl acetate ions, CH3COOCH3.+. The rate of molecular ion fragmentation with the loss of CH3O. and CH2OH radicals as a function of ion internal energy was obtained from the coincidence data and used in conjunction with Rice-Ramsperger-Kassel-Markus and ab initio molecular orbital calculations to model the dissociation/isomerization mechanism of the methyl acetate ion (A). The data were found to be consistent with the mechanism involving a hydrogen-bridged complex CH3CO[middle dot][middle dot][middle dot]H[middle dot][middle dot][middle dot]OCH2.+(E) as the direct precursor of the observed fragments CH3CO+ and CH2OH.. The two-component decay rates were modeled with a three-well-two-product potential energy surface including the distonic ion CH3C(OH)OCH2.+(B) and enol isomer CH2C(OH)OCH3.+(C), which are formed from the methyl acetate ion by two consecutive [1,4]-hydrogen shifts. The 0 K heats of formation of isomers B and C as well as transition states TSAB, TSBC, and TSBE (relative to isomer A) were calculated from Rice-Ramsperger-Kassel-Markus (RRKM) theory.
H.G. Schmidt (Henk); J. Cohen-Schotanus (Janke); H.T. van der Molen (Henk); T.A.W. Splinter (Ted); C. van den Bulte (Christophe); R. Holdrinet (Rob); H.J.M. van Rossum (Herman)
2010-01-01
textabstractIn this article, an alternative for Tinto's integration theory of student persistence is proposed and tested. In the proposed theory, time available for individual study is considered a major determinant of both study duration and graduation rate of students in a particular curriculum.
Schmidt, H.G.; Cohen-Schotanus, J.; van der Molen, H.T.; Splinter, T.A.W.; Bulte, J.; Holdrinet, R.; van Rossum, H.J.M.
In this article, an alternative for Tinto's integration theory of student persistence is proposed and tested. In the proposed theory, time available for individual study is considered a major determinant of both study duration and graduation rate of students in a particular curriculum. In this view,
Schmidt, Henk G.; Cohen-Schotanus, Janke; van der Molen, Henk T.; Splinter, Ted A. W.; Bulte, Jan; Holdrinet, Rob; van Rossum, Herman J. M.
2010-01-01
In this article, an alternative for Tinto's integration theory of student persistence is proposed and tested. In the proposed theory, time available for individual study is considered a major determinant of both study duration and graduation rate of students in a particular curriculum. In this view, other activities in the curriculum, in…
Temperature and Pressure Dependence of the Reaction S plus CS (+M) -> CS2 (+M)
DEFF Research Database (Denmark)
Glarborg, Peter; Marshall, Paul; Troe, Juergen
2015-01-01
Experimental data for the unimolecular decomposition of CS2 from the literature are analyzed by unimolecular rate theory with the goal of obtaining rate constants for the reverse reaction S + CS (+M) -> CS2 (+M) over wide temperature and pressure ranges. The results constitute an important input...
Ramírez-Anguita, Juan M; González-Lafont, Àngels; Lluch, José M
2011-07-30
The chemical tropospheric dimethyl sulfide (DMS, CH3SCH3) degradation involves several steps highly dependent on the environmental conditions. So, intensive efforts have been devoted during the last years to enhance the understanding of the DMS oxidation mechanism under different conditions. The reaction of DMS with OH is considered to be the most relevant process that initiates the whole oxidation process. The experimental observations have been explained by a two-channel mechanism consisting of a H-abstraction process leading to CH3S(O)CH3 and HO2 and an addition reaction leading to the DMS·OH adduct. In the presence of O2, the DMS·OH adduct is competitively scavenged increasing the contribution of the addition channel to the overall DMS oxidation. Recent experimental measurements have determined from a global fit that the rate constant of this scavenging process is independent of pressure and temperature but this rate constant cannot be directly measured. In this article, a variational transition-state theory calculation of the low- and high-pressure rate constants for the reaction between DMS·OH and O2 has been carried out as a function of temperature. Our proposal is that the slight temperature dependence of the scavenging rate constant can only be explained if the H-abstraction bottleneck is preceded by a dynamical bottleneck corresponding to the association process between the DMS·OH adduct and the O2 molecule. The agreement between the low-pressure and high-pressure rate constants confirms the experimental observations. Copyright © 2011 Wiley Periodicals, Inc.
Standage, Martyn; Duda, Joan L; Ntoumanis, Nikos
2006-03-01
In the present study, we used a model of motivation grounded in self-determination theory (Deci & Ryan, 1985, 1991; Ryan & Deci, 2000a, 2000b, 2002) to examine the relationship between physical education (PE) students' motivational processes and ratings of their effort and persistence as provided by their PE teacher. Data were obtained from 394 British secondary school students (204 boys, 189 girls, 1 gender not specified; M age = 11.97 years; SD = .89; range = 11-14 years) who responded to a multisection inventory (tapping autonomy-support, autonomy, competence, relatedness, and self-determined motivation). The students' respective PE teachers subsequently provided ratings reflecting the effort and persistence each student exhibited in their PE classes. The hypothesized relationships among the study variables were examined via structural equation modeling analysis using latent factors. Results of maximum likelihood analysis using the bootstrapping method revealed the proposed model demonstrated a good fit to the data, chi-squared (292) = 632.68, p self-determination. Student-reported levels of self-determined motivation positively predicted teacher ratings of effort and persistence in PE. The findings are discussed with regard to enhancing student motivation in PE settings.
Hao, Tian; Xu, Yuanze; Hao, Ting
2018-04-01
The Eyring's rate process theory and free volume concept are employed to treat protons (or other particles) transporting through a 2D (two dimensional) crystal like graphene and hexagonal boron nitride. The protons are assumed to be activated first in order to participate conduction and the conduction rate is dependent on how much free volume available in the system. The obtained proton conductivity equations show that only the number of conduction protons, proton size and packing structure, and the energy barrier associated with 2D crystals are critical; the quantization conductance is unexpectedly predicted with a simple Arrhenius type temperature dependence. The predictions agree well with experimental observations and clear out many puzzles like much smaller energy barrier determined from experiments than from the density function calculations and isotope separation rate independent of the energy barrier of 2D crystals, etc. Our work may deepen our understandings on how protons transport through a membrane and has direct implications on hydrogen related technology and proton involved bioprocesses.
Using Omega and NIF to Advance Theories of High-Pressure, High-Strain-Rate Tantalum Plastic Flow
Rudd, R. E.; Arsenlis, A.; Barton, N. R.; Cavallo, R. M.; Huntington, C. M.; McNaney, J. M.; Orlikowski, D. A.; Park, H.-S.; Prisbrey, S. T.; Remington, B. A.; Wehrenberg, C. E.
2015-11-01
Precisely controlled plasmas are playing an important role as both pump and probe in experiments to understand the strength of solid metals at high energy density (HED) conditions. In concert with theory, these experiments have enabled a predictive capability to model material strength at Mbar pressures and high strain rates. Here we describe multiscale strength models developed for tantalum and vanadium starting with atomic bonding and extending up through the mobility of individual dislocations, the evolution of dislocation networks and so on up to full scale. High-energy laser platforms such as the NIF and the Omega laser probe ramp-compressed strength to 1-5 Mbar. The predictions of the multiscale model agree well with the 1 Mbar experiments without tuning. The combination of experiment and theory has shown that solid metals can behave significantly differently at HED conditions; for example, the familiar strengthening of metals as the grain size is reduced has been shown not to occur in the high pressure experiments. Work performed under the auspices of the U.S. Dept. of Energy by Lawrence Livermore National Lab under contract DE-AC52-07NA273.
Schröder, Detlef; Herrmann, W. A.; Fischer, Richard W.; Schwarz, Helmut
1992-12-01
The unimolecular chemistry of CH3ReO[radical sign]+3 in the gas phase commences with a methyl migration to' generate CH3 OReO[radical sign]+2. This further undergoes multiple hydrogen migration to the metal centre to generate an intermediate which serves as a precursor for the elimination of both molecular hydrogen and of carbon monoxide. If CH3ReO[radical sign]+3 is reacted with ethylene, inter alia products are observed which point to a competition between an intramolecular metathesis reaction of the ethylene-inserted intermediate CH3CH2CH2ReO3[radical sign]+ and epoxidation of ethylene to generate c-C2H4O.
International Nuclear Information System (INIS)
Hong, Sungjun; Chung, Yanghon; Woo, Chungwon
2015-01-01
South Korea, as the 9th largest energy consuming in 2013 and the 7th largest greenhouse gas emitting country in 2011, established ‘Low Carbon Green Growth’ as the national vision in 2008, and is announcing various active energy policies that are set to gain the attention of the world. In this paper, we estimated the decrease of photovoltaic power generation cost in Korea based on the learning curve theory. Photovoltaic energy is one of the leading renewable energy sources, and countries all over the world are currently expanding R and D, demonstration and deployment of photovoltaic technology. In order to estimate the learning rate of photovoltaic energy in Korea, both conventional 1FLC (one-factor learning curve), which considers only the cumulative power generation, and 2FLC, which also considers R and D investment were applied. The 1FLC analysis showed that the cost of power generation decreased by 3.1% as the cumulative power generation doubled. The 2FCL analysis presented that the cost decreases by 2.33% every time the cumulative photovoltaic power generation is doubled and by 5.13% every time R and D investment is doubled. Moreover, the effect of R and D investment on photovoltaic technology took after around 3 years, and the depreciation rate of R and D investment was around 20%. - Highlights: • We analyze the learning effects of photovoltaic energy technology in Korea. • In order to calculate the learning rate, we use 1FLC (one-factor learning curve) and 2FLC methods, respectively. • 1FLC method considers only the cumulative power generation. • 2FLC method considers both cumulative power generation and knowledge stock. • We analyze a variety of scenarios by time lag and depreciation rate of R and D investment
Razeto-Barry, Pablo; Díaz, Javier; Vásquez, Rodrigo A
2012-06-01
The general theories of molecular evolution depend on relatively arbitrary assumptions about the relative distribution and rate of advantageous, deleterious, neutral, and nearly neutral mutations. The Fisher geometrical model (FGM) has been used to make distributions of mutations biologically interpretable. We explored an FGM-based molecular model to represent molecular evolutionary processes typically studied by nearly neutral and selection models, but in which distributions and relative rates of mutations with different selection coefficients are a consequence of biologically interpretable parameters, such as the average size of the phenotypic effect of mutations and the number of traits (complexity) of organisms. A variant of the FGM-based model that we called the static regime (SR) represents evolution as a nearly neutral process in which substitution rates are determined by a dynamic substitution process in which the population's phenotype remains around a suboptimum equilibrium fitness produced by a balance between slightly deleterious and slightly advantageous compensatory substitutions. As in previous nearly neutral models, the SR predicts a negative relationship between molecular evolutionary rate and population size; however, SR does not have the unrealistic properties of previous nearly neutral models such as the narrow window of selection strengths in which they work. In addition, the SR suggests that compensatory mutations cannot explain the high rate of fixations driven by positive selection currently found in DNA sequences, contrary to what has been previously suggested. We also developed a generalization of SR in which the optimum phenotype can change stochastically due to environmental or physiological shifts, which we called the variable regime (VR). VR models evolution as an interplay between adaptive processes and nearly neutral steady-state processes. When strong environmental fluctuations are incorporated, the process becomes a selection model
Hao, Tian
2015-02-28
The tap density of a granular powder is often linked to the flowability via the Carr index that measures how tight a powder can be packed, under an assumption that more easily packed powders usually flow poorly. Understanding how particles are packed is important for revealing why a powder flows better than others. There are two types of empirical equations that were proposed to fit the experimental data of packing fractions vs. numbers of taps in the literature: the inverse logarithmic and the stretched exponential. Using the rate process theory and the free volume concept under the assumption that particles will obey similar thermodynamic laws during the tapping process if the "granular temperature" is defined in a different way, we obtain the tap density equations, and they are reducible to the two empirical equations currently widely used in literature. Our equations could potentially fit experimental data better with an additional adjustable parameter. The tapping amplitude and frequency, the weight of the granular materials, and the environmental temperature are grouped into this parameter that weighs the pace of the packing process. The current results, in conjunction with our previous findings, may imply that both "dry" (granular) and "wet" (colloidal and polymeric) particle systems are governed by the same physical mechanisms in term of the role of the free volume and how particles behave (a rate controlled process).
Directory of Open Access Journals (Sweden)
R. TAMBORINI
2013-12-01
Full Text Available Dopo la fine del sistema di fede, di Bretton Woods in un regime di cambio liberamente fluttuante, e in particolare la completa politica di laissez-faire degli Stati Uniti dopo il 1980, è stata sostenuta da una letteratura vasta e influente - la cosiddetta "teoria il punto della cambio "- che ha avuto predominio quasi assoluto nel campo. Il presente lavoro è di natura teorica in primo luogo, richiamando l'attenzione sul recente cambiamento drastico di opinione per quanto riguarda l'efficienza dei mercati dei cambi, delle aspettative e speculazioni. In contrasto con la credenza precedentemente detenuta, gli agenti che anticipano il mercato sono ora accusati di inefficiente, se non il comportamento irrazionale; si dice che essere mal interpretare o violare i "dati concreti", che dovrebbero portare il mercato sul sentiero di equilibrio. Secondo l'autore, questa nuova vena è impegnativo, ma il nuovo "cattivo" deus ex machina è convincente come i suoi predecessori "buoni". Così, l'attenzione è proprio sui fattori fondamentali della dinamica dei tassi di cambio nel contesto attuale di finanza integrata Lowing the end of the Bretton Woods system faith in a freely floating exchange rate regime, and in particular the complete Laissez-faire policy of the US after 1980, was supported by a large and influential literature - the so-called "stock theory of the exchange rate" - which has had almost absolute dominance in the field. The present work is of primarily a theoretical nature, calling attention to the recent drastic change of opinion regarding the efficiency of foreign exchange markets, of expectations and speculation. In contrast to the previously held belief, agents that anticipate the market are now accused of inefficient, if not irrational behaviour; they are said to be misinterpreting or violating the "hard data" that should lead the market on the path of equilibrium. According to the author, this new vein is challenging, yet the new "bad
Study of the unimolecular decompositions of the (C3H6)+2 and (c-C3H6)+2 complexes
International Nuclear Information System (INIS)
Tzeng, W.; Ono, Y.; Linn, S.H.; Ng, C.Y.
1985-01-01
The major product channels identified in the unimolecular decompositions ofC 3 H + 6 xC 3 H 6 and c-C 3 H + 6 xc-C 3 H 6 in the total energy [neutral (C 3 H 6 ) 2 or (c-C 3 H 6 ) 2 heat of formation plus excitation energy] range of approx.230--450 kcal/mol are C 3 H + 7 +C 3 H 5 , C 4 H + 7 +C 2 H 5 , C 4 H + 8 +C 2 H 4 , and C 5 H + 9 +CH 3 . The measured appearance energy for C 4 H + 7 (9.54 +- 0.04 eV) from (C 3 H 6 ) 2 is equal to the thermochemical threshold for the formation of C 4 H + 7 +C 2 H 5 from (C 3 H 6 ) 2 , indicating that the exit potential energy barrier for the ion--molecule reaction C 3 H + 6 +C 3 H 6 →C 4 H + 7 +C 2 H 5 is negligible. There is evidence that the formations of C 4 H + 7 +C 2 H 4 +H from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 also proceed with high probabilities when they are energetically allowed. The variations of the relative abundances for C 4 H + 7 ,C 4 H + 8 , and C 5 H + 9 from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 as a function of ionizing photon energy are in qualitative agreement, suggesting that (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 rearrange to similar C 6 H + 12 isomers prior to fragmentation. The fact that C 6 H + 11 is found to be a primary ion from the unimolecular decomposition of (c-C 3 H 6 ) + 2 but not (C 3 H 6 ) + 2 supports the conclusion that the distribution of C 6 H + 12 collision complexes involved in the C 3 H + 6 +C 3 H 6 reactions is different from that in the cyclopropane ion--molecule reactions
Nicolini, Paola; Ciulla, Michele M; De Asmundis, Carlo; Magrini, Fabio; Brugada, Pedro
2012-05-01
Heart rate variability (HRV) is the temporal beat-to-beat variation in successive RR intervals on an electrocardiographic (ECG) recording and it reflects the regulation of the heart rate (HR) by the autonomic nervous system (ANS). HRV analysis is a noninvasive tool for the assessment of autonomic function that gained momentum in the late 1980s when its clinical relevance as a predictor of mortality was established by a milestone study by Kleiger et al. in patients with postacute myocardial infarction. In the last few decades, the increasing availability of commercial ECG devices offering HRV analysis has made HRV a favorite marker for risk stratification in the setting of cardiovascular disease. The rapid aging of the world population and the growing popularity of HRV have also fueled interest for the prognostic value of HRV in the elderly, outside a specific cardiological context. However, the discussion of HRV measures in the elderly is still very much centered on the rather reductionistic model of sympathovagal balance, with the orthosympathetic and parasympathetic limbs of the ANS exercising opposing effects on the heart via autonomic tone. The expanding application of nonlinear dynamics to medicine has brought to the forefront the notion of system complexity, embedded in the mathematical concepts of chaos theory and fractals, and provides an opportunity to suggest a broader interpretation for the prognostic significance of HRV, especially in the elderly. Although the use of novel indices of HRV may be hampered by practical issues, a more holistic approach to HRV may still be safeguarded if traditional time- and frequency-domain measures are viewed in terms of autonomic modulation. This review focuses on HRV in geriatric populations. It considers studies on the prognostic value of HRV in elderly subjects, discussing the potential confounding effect of erratic rhythm, and concentrates on the conceptual distinction between autonomic tone and autonomic modulation
Pawlak, Mariusz; Ben-Asher, Anael; Moiseyev, Nimrod
2018-01-09
We present a simple expression and its derivation for reaction rate coefficients for cold anisotropic collision experiments based on adiabatic variational theory and time-independent non-Hermitian scattering theory. We demonstrate that only the eigenenergies of the resulting one-dimensional Schrödinger equation for different complex adiabats are required. The expression is applied to calculate the Penning ionization rate coefficients of an excited metastable helium atom with molecular hydrogen in an energy range spanning from hundreds of kelvins down to the millikelvin regime. Except for trivial quantities like the masses of the nuclei and the bond length of the diatomic molecule participating in the collision, one needs as input data only the complex potential energy surface (CPES). In calculations, we used recently obtained ab initio CPES by D. Bhattacharya et al. ( J. Chem. Theory Comput. 2017 , 13 , 1682 - 1690 ) without fitting parameters. The results show good accord with current measurements ( Nat. Phys. 2017 , 13 , 35 - 38 ).
Chang, Tsun-Mei; Dang, Liem X.
2017-10-01
Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found that the residence times of EC around Li+ ions varied from 60 to 450 ps, depending on the correction method used. We found that the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influences the dissociation kinetics of ion pairing.
Collazo, Andrés A.
2018-01-01
A model derived from the theory of planned behavior was empirically assessed for understanding faculty intention to use student ratings for teaching improvement. A sample of 175 professors participated in the study. The model was statistically significant and had a very large explanatory power. Instrumental attitude, affective attitude, perceived…
Rate theory of solvent exchange and kinetics of Li+ − BF4−/PF6− ion pairs in acetonitrile
International Nuclear Information System (INIS)
Dang, Liem X.; Chang, Tsun-Mei
2016-01-01
In this paper, we describe our efforts to apply rate theories in studies of solvent exchange around Li + and the kinetics of ion pairings in lithium-ion batteries (LIBs). We report one of the first computer simulations of the exchange dynamics around solvated Li + in acetonitrile (ACN), which is a common solvent used in LIBs. We also provide details of the ion-pairing kinetics of Li + -[BF 4 ] and Li + -[PF 6 ] in ACN. Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ACN exchange process between the first and second solvation shells around Li + . We calculate exchange rates using transition state theory and weighted them with the transmission coefficients determined by the reactive flux, Impey, Madden, and McDonald approaches, and Grote-Hynes theory. We found the relaxation times changed from 180 ps to 4600 ps and from 30 ps to 280 ps for Li + -[BF 4 ] and Li + -[PF 6 ] ion pairs, respectively. These results confirm that the solvent response to the kinetics of ion pairing is significant. Our results also show that, in addition to affecting the free energy of solvation into ACN, the anion type also should significantly influence the kinetics of ion pairing. These results will increase our understanding of the thermodynamic and kinetic properties of LIB systems.
Onuki, Y.; Hibiya, T.
2016-02-01
The baroclinic tides are thought to be the dominant energy source for turbulent mixing in the ocean interior. In contrast to the geography of the energy conversion rates from the barotropic to baroclinic tides, which has been clarified in recent numerical studies, the global distribution of the energy sink for the resulting low-mode baroclinic tides remains obscure. A key to resolve this issue is the resonant wave-wave interactions, which transfer part of the baroclinic tidal energy to the background internal wave field enhancing the local energy dissipation rates. Recent field observations and numerical studies have pointed out that parametric subharmonic instability (PSI), one of the resonant interactions, causes significant energy sink of baroclinic tidal energy at mid-latitudes. The purpose of this study is to analyze the quantitative aspect of PSI to demonstrate the global distribution of the intensity of resonant wave interactions, namely, the attenuation rate of low-mode baroclinic tidal energy. Our approach is basically following the weak turbulence theory, which is the standard theory for resonant wave-wave interactions, where techniques of singular perturbation and statistical physics are employed. This study is, however, different from the classical theory in some points; we have reformulated the weak turbulence theory to be applicable to low-mode internal waves and also developed its numerical calculation method so that the effects of stratification profile and oceanic total depth can be taken into account. We have calculated the attenuation rate of low-mode baroclinic tidal waves interacting with the background Garrett-Munk internal wave field. The calculated results clearly show the rapid attenuation of baroclinic tidal energy at mid-latitudes, in agreement with the results from field observations and also show the zonal inhomogeneity of the attenuation rate caused by the density structures associated with the subtropical gyre. This study is expected
International Nuclear Information System (INIS)
McGrail, B. PETER; Icenhower, Jonathan P.; Rodriguez, Elsa A.; McGrail, B.P.; Cragnolino, G.A.
2002-01-01
Discrepancies between classical kinetic rate law theory and experiment were quantitatively assessed and found to correlate with macromolecular amorphous separation in the sodium borosilicate glass system. A quantitative reinterpretation of static corrosion data and new SPFT data shows that a recently advanced protective surface layer theory fails to describe the observed dissolution behavior of simple and complex silicate glasses under carefully controlled experimental conditions. The hypothesis is shown to be self-inconsistent in contrast with a phase separation model that is in quantitative agreement with experiments
International Nuclear Information System (INIS)
Franca Walter, F.L.; Alvim, A.C.M.; Silva, F.C. da; Melo e Frutuoso, P.F.
1995-01-01
The application of the GPT methodology to a reliability engineering problem of great practical interest is discussed: that of the analysis of the influence of the demand rate on the accident rate of a process plant equipped with a single protective channel. This problem has been solved in the literature by traditional methods, that is, for each demand rate value the system of differential equations that governs the system behavior (derived from a Markovian reliability model) is solved and the resulting points are employed to generate the desired curve. This sensitivity analysis has been performed by means of a GPT approach in order to show how it could simplify the calculations. Although an analytical solution is available for the above equations, the application of the GPT approach needed the solution of the system for a few points (reference solutions) and the results agree very well with those published. (author). 9 refs, 4 figs
Falivene, Laura; Barone, Vincenzo; Talarico, Giovanni
2018-01-01
by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement
Wang, Yongqiang; Nunez, Felipe; Doyle III, Francis J.
2012-01-01
This paper addresses the synchronization rate of weakly connected pulse-coupled oscillators (PCOs). We prove that besides coupling strength, the phase response function is also a determinant of synchronization rate. Inspired by the result, we propose to increase the synchronization rate of PCOs by designing the phase response function. This has important significance in PCO-based clock synchronization of wireless networks. By designing the phase response function, synchronization rate is incr...
Experimental and theoretical examples of the value and limitations of transition state theory
International Nuclear Information System (INIS)
Golden, D.M.
1979-01-01
Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the ''direct'' reactions CH 3 + CH 3 CHO → CH 4 + CH 3 CO (1) and O + CH 4 → OH + CH 3 (2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of ''complex'' vs ''direct'' mechanisms. The reaction OH + CO → CO 2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted. 2 figures, 5 tables
Experimental and theoretical examples of the value and limitations of transition state theory
Golden, D. M.
1979-01-01
Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the 'direct' reactions CH3 + CH3CHO yields CH4 + CH3CO(1) and O + CH4 yields OH + CH3(2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of 'complex' vs. 'direct' mechanisms. The reaction OH + CO yields CO2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted.
Wang, Yongqiang; Núñez, Felipe; Doyle, Francis J
2012-07-25
This paper addresses the synchronization rate of weakly connected pulse-coupled oscillators (PCOs). We prove that besides coupling strength, the phase response function is also a determinant of synchronization rate. Inspired by the result, we propose to increase the synchronization rate of PCOs by designing the phase response function. This has important significance in PCO-based clock synchronization of wireless networks. By designing the phase response function, synchronization rate is increased even under a fixed transmission power. Given that energy consumption in synchronization is determined by the product of synchronization time and transformation power, the new strategy reduces energy consumption in clock synchronization. QualNet experiments confirm the theoretical results.
International Nuclear Information System (INIS)
Chandler, D.W.; Farneth, W.E.; Zare, R.N.
1982-01-01
The use of optoacoustic spectroscopy permits both the monitoring of the overtone excitation of t-butylhydroperoxide (t-BuOOH) and the in situ detection of the resulting reaction product t-butanol (t-BuOH). The sample is contained in a reaction cell, equipped with a microphone, in which all surfaces have been specially passivated. The cell is placed inside the cavity of a dye laser tuned to excite the 5--0 O--H stretch of the t-BuOOH at 619.0 nm. The dissociation process yields directly xOH and t-BuOx, and the latter readily abstracts a hydrogen atom from a parent molecule to form t-butanol (t-BuOH). The appearance rate of t-BuOH is obtained by ratioing the area under the 5--0 O--H stretch of t-BuOH to that of a combination band of t-BuOOH. At low pressures, below 40 Torr, a plot of the reciprocal of the t-BuOH appearance rate versus total pressure shows near linear behavior. This linearlity can be well described by a statistical model (RRKM) when careful averaging of the dissociation rate over the thermal energy distribution of the photoactivated molecules is included. At pressures above 40 Torr, a marked deviation from linearity appears. This deviation is fit to a kinetic model in which the dissociation rate of an energy nonrandomized molecule competes with the rate of intramolecular energy relaxation. This places a lower bound of > or =5.0 x 10 11 s -1 on the rate of energy randomization. A discussion of this model in the context of other possible kinetic schemes as well as other photoactivated and chemically activated systems is presented
McPhillips, D. F.; Hoke, G. D.; Niedermann, S.; Wittmann, H.
2015-12-01
There is widespread interest in quantifying the growth and decay of topography. However, prominent methods for quantitative determinations of paleoelevation rely on assumptions that are often difficult to test. For example, stable isotope paleoaltimetry relies on the knowledge of past lapse rates and moisture sources. Here, we demonstrate how cosmogenic 10Be - 21Ne and/or 10Be - 26Al sample pairs can be applied to provide independent estimates of surface uplift rate using both published data and new data from the Atacama Desert. Our approach requires a priori knowledge of the maximum age of exposure of the sampled surface. Ignimbrite surfaces provide practical sampling targets. When erosion is very slow (roughly, ≤1 m/Ma), it is often possible to constrain paleo surface uplift rate with precision comparable to that of stable isotopic methods (approximately ±50%). The likelihood of a successful measurement is increased by taking n samples from a landscape surface and solving for one regional paleo surface uplift rate and n local erosion rates. In northern Chile, we solve for surface uplift and erosion rates using three sample groups from the literature (Kober et al., 2007). In the two lower elevation groups, we calculate surface uplift rates of 110 (+60/-12) m/Myr and 160 (+120/-6) m/Myr and estimate uncertainties with a bootstrap approach. The rates agree with independent estimates derived from stream profile analyses nearby (Hoke et al., 2007). Our calculated uplift rates correspond to total uplift of 1200 and 850 m, respectively, when integrated over appropriate timescales. Erosion rates were too high to reliably calculate the uplift rate in the third, high elevation group. New cosmogenic nuclide analyses from the Atacama Desert are in progress, and preliminary results are encouraging. In particular, a replicate sample in the vicinity of the first Kober et al. (2007) group independently yields a surface uplift rate of 110 m/Myr. Compared to stable isotope
International Nuclear Information System (INIS)
Stack, Andrew G.; Raiten, Paolo; Gale, Julian D.
2012-01-01
Mineral growth and dissolution are often treated as occurring via a single, reversible process that governs the rate of reaction. We show that multiple, distinct intermediate states can occur during both growth and dissolution. Specifically, we have used metadynamics, a method to efficiently explore the free energy landscape of a system, coupled to umbrella sampling and reactive flux calculations, to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped, barite (BaSO4) surface. The activation energies calculated for the rate limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous, non-steady state mineral reaction rates observed experimentally, and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.
Directory of Open Access Journals (Sweden)
Ali Khan-Jeihooni
2014-06-01
Full Text Available Introduction: Cesarean section is considered as a major surgery accompanied by several complications. The present study aimed to determine the effect of educational intervention based on the theory of reasoned action to reduce the rate of cesarean section among pregnant women in Fasa, Southern Iran. Materials and Methods: This quasi-experimental study was performed on 100 (50 participants in each of the control and intervention groups primiparous women in the third trimester of pregnancy admitted to health centers of Fasa city, Fars province, Iran. The data-gathering tool was a multipart questionnaire containing demographic variables and the theory of reasoned action structures. After the pretest, the intervention group underwent exclusive training based on the theory of reasoned action. Then, after 3 months, both groups took part in the posttest. Data was analyzed by paired T-test, independent T-test and chi-square using SPSS-18 software. Results: A significant difference was found between the two groups regarding knowledge, evaluations behavioral outcomes, Behavioral beliefs and intention (P<0.001. Chi-square analysis showed a significant difference between the two groups regarding their performance (P<0.001. Conclusion: The present intervention was effective in increasing the pregnant women’s knowledge, evaluation of outcomes, attitude and strengthening their intention as well as performance. Therefore, it is suggested to use this model and other systematic straining for pregnant women to decrease the rate of cesarean section.
International Nuclear Information System (INIS)
Katoh, Yutai; Stoller, Roger E.; Kohno, Yutaka; Kohyama, Akira
1994-01-01
A kinetic model was developed to investigate the influence of the displacement rate and helium generation rate on microstructural evolution in austenitic stainless steels. The model integrates the rate equations describing the evolution of point defects, small point defect clusters, helium-vacancy clusters, and the larger cavity size distribution that is responsible for observable swelling. Cavity (bubble) nucleation is accounted for by the helium-vacancy cluster evolution, while void formation occurs when bubbles grow beyond a critical size in the larger cavity distribution. A series of ion irradiation experiments were used to both calibrate the model and to provide a comparison between model predictions and experimental observations. The experiments involved single and dual-beam irradiations of solution annealed AISI-316 stainless steel at 873 K. The displacement rates were in the range of 2x10 -3 to 1x10 -2 dpa/s and the helium-to-dpa ratios were in the range of 0 to 50 appm He/dpa. The maximum displacement dose was 25 dpa. The experiments revealed a significant effect of helium on both the dislocation structure and the cavity distribution. The model predictions of helium effects over a broad range of He/dpa ratios and displacement rates were consistent with experimental observations. ((orig.))
Directory of Open Access Journals (Sweden)
K. Y. Lin
2013-03-01
Full Text Available Zooplankton play an essential role in marine food webs, and understanding how community-level growth rates of zooplankton vary in the field is critical for predicting how marine ecosystem function may vary in the face of environmental changes. Here, we used the artificial cohort method to examine the effects of temperature, body size, and chlorophyll concentration (a proxy for food on weight-specific growth rates for copepod communities in the East China Sea. Specifically, we tested the hypothesis that copepod community growth rates can be described by the metabolic theory of ecology (MTE, linking spatio-temporal variation of copepod growth rate with temperature and their body size. Our results generally agree with predictions made by the MTE and demonstrate that weight-specific growth rates of copepod communities in our study area are positively related with temperature and negatively related to body size. However, the regression coefficients of body size do not approach the theoretical predictions. Furthermore, we find that the deviation from the MTE predictions may be partly attributed to the effect of food availability (which is not explicitly accounted for by the MTE. In addition, significant difference in the coefficients of temperature and body size exists among taxonomic groups. Our results suggest that considering the effects of food limitation and taxonomy is necessary to better understand copepod growth rates under in situ conditions, and such effects on the MTE-based predictions need further investigation.
Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei
2017-11-30
The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.
Non-equilibrium reaction rates in chemical kinetic equations
Gorbachev, Yuriy
2018-05-01
Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.
NMR relaxation rates and Knight shifts in MgB2 and AlB2: theory versus experiments
International Nuclear Information System (INIS)
Pavarini, E; Baek, S H; Suh, B J; Borsa, F; Bud'ko, S L; Canfield, P C
2003-01-01
We have performed 11 B NMR measurements in 11 B enriched MgB 2 powder sample in the normal phase. The Knight shift was accurately determined by using the magic angle spinning technique. Results for 11 B and 27 Al Knight shifts (K) and relaxation rates (1/T 1 ) are also reported for AlB 2 . The data show a dramatic decrease of both K and 1/T 1 for 11 B in AlB 2 with respect to MgB 2 . We compare experimental results with ab initio calculated NMR relaxation rates and Knight shifts. The experimental values for 1/T 1 and K are in most cases in good agreement with the theoretical results. We show that the decrease of K and 1/T 1 for 11 B is consistent with a drastic drop of the density of states at the boron site in AlB 2 with respect to MgB 2
DEFF Research Database (Denmark)
Bork, Nicolai Christian; Kurten, T.; Enghoff, Martin Andreas Bødker
2011-01-01
Based on density functional theory calculations we present a study of the gaseous oxidation of SO2 to SO3 by an anionic O3−(H2On cluster, n=0–5. The configurations of the most relevant reactants, transition states, and products are discussed and compared to previous findings. Two different classes......, the most energetically favorable class of transition states vary with the number of water molecules attached. A kinetic model is utilized, taking into account the most likely outcomes of the initial SO2O3−(H2O)n collision complexes. This model shows that the reaction takes place at collision rates...
International Nuclear Information System (INIS)
Fort, J.; Cukrowski, A.S.
1998-01-01
The effect of the heat flux on the rate of chemical reaction in dilute gases is shown to be important for reactions characterized by high activation energies and in the presence of very large temperature gradients. This effect, obtained from the second-order terms in the distribution function (similar to those obtained in the Burnett approximation to the solution of the Boltzmann equation), is derived on the basis of information theory. It is shown that the analytical results describing the effect are simpler if the kinetic definition for the nonequilibrium temperature is introduced than if the thermodynamic definition is introduced. The numerical results are nearly the same for both definitions. (author)
International Nuclear Information System (INIS)
Xaplanteris, Constantine L.; Filippaki, Eleni D.
2013-01-01
During the last decades many researchers have been occupied with other plasma applications apart from the big challenge which the thermonuclear fusion poses. Many experiments have been carried out on the plasma behavior in contact with a solid surface; when the surface material consists of chemical compounds (e.g. oxides of metals), then the plasma chemistry takes place. The present paper contains the final experimental and theoretical work of Plasma Laboratory at “Demokritos , which consists of an elaboration of plasma sheath parameters adapted to experimental conditions, a suitable choice of plasma gases (either H 2 or N 2 ), and an electric potential current enforcement on objects. Additionally, a brief theory is given to explain the results, with a short reference to both boundary phenomena in thermonuclear reactors and low pressure plasma of glow discharges, so as to reveal the similarities and differences of these two cases. An extensive examination of the treated objects by X-ray diffraction method (XRD) gives results in agreement with the theoretical predictions. Using this improvement on plasma restoration system, (a combination of electric current on metallic object into suitable plasma), it is shown that better results can be achieved on the cleaning and conservation of archaeological objects. (plasma technology)
Jami-Alahmadi, Yasaman; Linford, Bryan D; Fridgen, Travis D
2016-12-29
The unimolecular chemistries and structures of gas-phase (ProLeu)M + and (LeuPro)M + complexes when M = Li, Na, Rb, and Cs have been explored using a combination of SORI-CID, IRMPD spectroscopy, and computational methods. CID of both (LeuPro)M + and (ProLeu)M + showed identical fragmentation pathways and could not be differentiated. Two of the fragmentation routes of both peptides produced ions at the same nominal mass as (Pro)M + and (Leu)M + , respectively. For the litiated peptides, experiments revealed identical IRMPD spectra for each of the m/z 122 and 138 ions coming from both peptides. Comparison with computed IR spectra identified them as the (Pro)Li + and (Leu)Li + , and it is concluded that both zwitterionic and canonical forms of (Pro)Li + exist in the ion population from CID of both (ProLeu)Li + and (LeuPro)Li + . The two isomeric peptide complexes could be distinguished using IRMPD spectroscopy in both the fingerprint and the CH/NH/OH regions. The computed IR spectra for the lowest energy structures of each charge solvated complexes are consistent with the IRMPD spectra in both regions for all metal cation complexes. Through comparison between the experimental spectra, it was determined that in lithiated and sodiated ProLeu, metal cation is bound to both carbonyl oxygens and the amine nitrogen. In contrast, the larger metal cations are bound to the two carbonyls, while the amine nitrogen is hydrogen bonded to the amide hydrogen. In the lithiated and sodiated LeuPro complexes, the metal cation is bound to the amide carbonyl and the amine nitrogen while the amine nitrogen is hydrogen bonded to the carboxylic acid carbonyl. However, there is no hydrogen bond in the rubidiated and cesiated complexes; the metal cation is bound to both carbonyl oxygens and the amine nitrogen. Details of the position of the carboxylic acid C═O stretch were especially informative in the spectroscopic confirmation of the lowest energy computed structures.
Marcus, R. A.
1962-01-01
Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)
THE OPTIMAL RATE OF R&D EXPENDITURES ÎN GDP – BETWEEN THEORY AND PRACTICE
Directory of Open Access Journals (Sweden)
Steliana SANDU
2010-12-01
Full Text Available The relation between economic growth, competitiveness, productivity, on one hand, and investment in research and development (R&D, on the other, has been the research subject of numerous scientific studies. The significant contribution of the investment in R&D to productivity growth, competitiveness and economic growth is generally acknowledged. Some authors have attempted to empirically and theoretically estimate the optimal level of R&D investment at the micro and mezo level, following different paths, according to their option for the aggregation level of analysis or to the different indicators selected as most relevant. Yet, the identification of the R&D investment level that maximizes the productivity growth rate at macroeconomic level seems to have been rather marginal to the general research interest. Available scientific papers estimate it by relating the share of R&D spending in GDP to productivity, expressed through the Total Factor Productivity or labour productivity per hour worked. This paper looks into the correlation between the spending for research and development in some EU countries, as a share of GDP, underlining the relative positions to the optimal interval for R&D investment, according to Mario Coccia estimations, and the corresponding rates of labour productivity growth, during the 2000-2009 period. Special attention will be given to Romania’s positioning in European context, in order to identify potential solutions to future improvement.
International Nuclear Information System (INIS)
Nigmatulin, B.I.; Soplenkov, K.I.
1978-01-01
On the basis of the concepts of two-phase dispersive flow with various structures (bubble, vapour-drop etc) in the framework of the two-speed and two-temperature one-dimension stationary model of the current with provision for phase transitions the conditions, under which a critical (maximum) flow rate of two-phase mixture is achieved during its outflowing from a channel with the pre-set geometry, have been determined. It is shown, that for the choosen set of two-phase flow equations with the known parameters of deceleration and structure one of the critical conditions is satisfied: either solution of the set of equations corresponding a critical flow rate is a special one, i.e. passes through a special point locating between minimum and outlet channel sections where the carrying phase velocity approaches the value of decelerated sound speed in the mixture or the determinator of the initial set of equations equals zero for the outlet channel sections, i.e. gradients of the main flow parameters tend to +-infinity in this section, and carrying phase velocity also approaches the value of the decelerated sound velocity in the mixture
International Nuclear Information System (INIS)
Yamachi, Jun
2007-01-01
This study was performed to evaluate the effects in the title on TDC (time-density curve) using a phantom. CT machine used was Toshiba Aquilion Multi 64, TDC phantom was the product of Nemoto-Kyorindo Co., and the contrast medium was Eisai iomeprol, in syringe-sealed formulations of 300 and 350 mg I/mL. The medium was infused at 1-5 mL/sec in the phantom equivalent to body weight of 78 kg (total water volume=1 min circulation=6,000 mL, 800 mL/heart) to obtain 30 TDCs. Evaluated were the relationships of the infusion rate (mL/sec), volume (mL) or time (sec) with TDC parameters of the detection time of the medium, slope, time to reach the maximum CT value, the maximum CT value, time to keep the CT concentration and its actual concentration. Results revealed that, regardless to the difference of formulations of the contrast medium, TDC with high reproducibility can be obtainable by making the infusion rate of I per unit time and body weight (mgI/sec/kg) constant when the infusion time is made identical for CT of the same diagnostic purpose. (R.T.)
Kröner, Nico; Kotlarski, Sven; Fischer, Erich; Lüthi, Daniel; Zubler, Elias; Schär, Christoph
2017-05-01
Climate models robustly project a strong overall summer warming across Europe showing a characteristic north-south gradient with enhanced warming and drying in southern Europe. However, the processes that are responsible for this pattern are not fully understood. We here employ an extended surrogate or pseudo-warming approach to disentangle the contribution of different mechanisms to this response pattern. The basic idea of the surrogate technique is to use a regional climate model and apply a large-scale warming to the lateral boundary conditions of a present-day reference simulation, while maintaining the relative humidity (and thus implicitly increasing the specific moisture content). In comparison to previous studies, our approach includes two important extensions: first, different vertical warming profiles are applied in order to separate the effects of a mean warming from lapse-rate effects. Second, a twin-design is used, in which the climate change signals are not only added to present-day conditions, but also subtracted from a scenario experiment. We demonstrate that these extensions provide an elegant way to separate the full climate change signal into contributions from large-scale thermodynamic (TD), lapse-rate (LR), and circulation and other remaining effects (CO). The latter in particular include changes in land-ocean contrast and spatial variations of the SST warming patterns. We find that the TD effect yields a large-scale warming across Europe with no distinct latitudinal gradient. The LR effect, which is quantified for the first time in our study, leads to a stronger warming and some drying in southern Europe. It explains about 50 % of the warming amplification over the Iberian Peninsula, thus demonstrating the important role of lapse-rate changes. The effect is linked to an extending Hadley circulation. The CO effect as inherited from the driving GCM is shown to further amplify the north-south temperature change gradient. In terms of mean summer
Krstacic, Goran; Krstacic, Antonija; Smalcelj, Anton; Milicic, Davor; Jembrek-Gostovic, Mirjana
2007-04-01
Dynamic analysis techniques may quantify abnormalities in heart rate variability (HRV) based on nonlinear and fractal analysis (chaos theory). The article emphasizes clinical and prognostic significance of dynamic changes in short-time series applied on patients with coronary heart disease (CHD) during the exercise electrocardiograph (ECG) test. The subjects were included in the series after complete cardiovascular diagnostic data. Series of R-R and ST-T intervals were obtained from exercise ECG data after sampling digitally. The range rescaled analysis method determined the fractal dimension of the intervals. To quantify fractal long-range correlation's properties of heart rate variability, the detrended fluctuation analysis technique was used. Approximate entropy (ApEn) was applied to quantify the regularity and complexity of time series, as well as unpredictability of fluctuations in time series. It was found that the short-term fractal scaling exponent (alpha(1)) is significantly lower in patients with CHD (0.93 +/- 0.07 vs 1.09 +/- 0.04; P chaos theory during the exercise ECG test point out the multifractal time series in CHD patients who loss normal fractal characteristics and regularity in HRV. Nonlinear analysis technique may complement traditional ECG analysis.
Tajima, Satomi; Hayashi, Toshio; Hori, Masaru
2015-02-26
The rate coefficient of F2 + NO → F + FNO is 2 to 5 orders of magnitude higher than that of F2 + NO2 → F + FNO2 even though bond energies of FNO and FNO2 only differ by ∼0.2 eV. To understand the cause of having different rate coefficients of these two reactions, the change in total energies was calculated by varying the stereochemical arrangement of F2 with respect to NOx (x = 1 or 2) by the density functional theory (DFT), using CAM-B3LYP/6-311 G+(d) in the Gaussian program. The permitted approaching angle between the x-axis and the plane consisting of O, N, F, and ϕ plays a key role to restrict the reaction of NO2 and F2 compared to the reaction of NO and F2. This restriction in the reaction space is considered to be the main cause of different rate coefficients depending on the selection of x = 1 or 2 of the reaction of F2 + NOx → F + FNOx, which was also confirmed by the difference in Si etch rate using the F formed by those reactions.
Regueiro-Figueroa, Martín; Platas-Iglesias, Carlos
2015-06-18
We present a theoretical investigation of Gd-Owater bonds in different complexes relevant as contrast agents in magnetic resonance imaging (MRI). The analysis of the Ln-Owater distances, electron density (ρBCP), and electron localization function (ELF) at the bond critical points of [Ln(DOTA)(H2O)](-) and [Ln(DTPA-BMA)(H2O)] indicates that the strength of the Ln-Owater bonds follows the order DTPA-BMA > DOTA (M isomer) > DOTA (m isomer). The ELF values decrease along the 4f period as the Ln-Owater bonds get shorter, in line with the labile capping bond phenomenon. Extension of these calculations to other Gd(3+) complexes allowed us to correlate the experimentally observed water exchange rates and the calculated ρBCP and ELF values. The water exchange reaction becomes faster as the Gd-Owater bonds are weakened, which is reflected in longer bond distances and lower values of ρBCP and ELF. DKH2 calculations show that the two coordinated water molecules may also have significantly different (17)O hyperfine coupling constants (HFCCs).
Grima, R
2010-07-21
regions of parameter space in which there are maximum differences between the solutions of the master equation and the corresponding rate equations. We show that these differences depend sensitively on the Fano factors and on the inherent structure and topology of the chemical network. The theory of effective mesoscopic rate equations generalizes the conventional rate equations of physical chemistry to describe kinetics in systems of mesoscopic size such as biological cells.
Bacci, Elizabeth D; Staniewska, Dorota; Coyne, Karin S; Boyer, Stacey; White, Leigh Ann; Zach, Neta; Cedarbaum, Jesse M
2016-01-01
Our objective was to examine dimensionality and item-level performance of the Amyotrophic Lateral Sclerosis Functional Rating Scale-Revised (ALSFRS-R) across time using classical and modern test theory approaches. Confirmatory factor analysis (CFA) and Item Response Theory (IRT) analyses were conducted using data from patients with amyotrophic lateral sclerosis (ALS) Pooled Resources Open-Access ALS Clinical Trials (PRO-ACT) database with complete ALSFRS-R data (n = 888) at three time-points (Time 0, Time 1 (6-months), Time 2 (1-year)). Results demonstrated that in this population of 888 patients, mean age was 54.6 years, 64.4% were male, and 93.7% were Caucasian. The CFA supported a 4* individual-domain structure (bulbar, gross motor, fine motor, and respiratory domains). IRT analysis within each domain revealed misfitting items and overlapping item response category thresholds at all time-points, particularly in the gross motor and respiratory domain items. Results indicate that many of the items of the ALSFRS-R may sub-optimally distinguish among varying levels of disability assessed by each domain, particularly in patients with less severe disability. Measure performance improved across time as patient disability severity increased. In conclusion, modifications to select ALSFRS-R items may improve the instrument's specificity to disability level and sensitivity to treatment effects.
Han, Haoxue; Schlawitschek, Christiane; Katyal, Naman; Stephan, Peter; Gambaryan-Roisman, Tatiana; Leroy, Frédéric; Müller-Plathe, Florian
2017-05-30
We study the role of solid-liquid interface thermal resistance (Kapitza resistance) on the evaporation rate of droplets on a heated surface by using a multiscale combination of molecular dynamics (MD) simulations and analytical continuum theory. We parametrize the nonbonded interaction potential between perfluorohexane (C 6 F 14 ) and a face-centered-cubic solid surface to reproduce the experimental wetting behavior of C 6 F 14 on black chromium through the solid-liquid work of adhesion (quantity directly related to the wetting angle). The thermal conductances between C 6 F 14 and (100) and (111) solid substrates are evaluated by a nonequilibrium molecular dynamics approach for a liquid pressure lower than 2 MPa. Finally, we examine the influence of the Kapitza resistance on evaporation of droplets in the vicinity of a three-phase contact line with continuum theory, where the thermal resistance of liquid layer is comparable with the Kapitza resistance. We determine the thermodynamic conditions under which the Kapitza resistance plays an important role in correctly predicting the evaporation heat flux.
Buatois, Simon; Retout, Sylvie; Frey, Nicolas; Ueckert, Sebastian
2017-10-01
This manuscript aims to precisely describe the natural disease progression of Parkinson's disease (PD) patients and evaluate approaches to increase the drug effect detection power. An item response theory (IRT) longitudinal model was built to describe the natural disease progression of 423 de novo PD patients followed during 48 months while taking into account the heterogeneous nature of the MDS-UPDRS. Clinical trial simulations were then used to compare drug effect detection power from IRT and sum of item scores based analysis under different analysis endpoints and drug effects. The IRT longitudinal model accurately describes the evolution of patients with and without PD medications while estimating different progression rates for the subscales. When comparing analysis methods, the IRT-based one consistently provided the highest power. IRT is a powerful tool which enables to capture the heterogeneous nature of the MDS-UPDRS.
Prisciandaro, James J; Tolliver, Bryan K
2016-11-15
The Young Mania Rating Scale (YMRS) and Montgomery-Asberg Depression Rating Scale (MADRS) are among the most widely used outcome measures for clinical trials of medications for Bipolar Disorder (BD). Nonetheless, very few studies have examined the measurement characteristics of the YMRS and MADRS in individuals with BD using modern psychometric methods. The present study evaluated the YMRS and MADRS in the Systematic Treatment Enhancement Program for BD (STEP-BD) study using Item Response Theory (IRT). Baseline data from 3716 STEP-BD participants were available for the present analysis. The Graded Response Model (GRM) was fit separately to YMRS and MADRS item responses. Differential item functioning (DIF) was examined by regressing a variety of clinically relevant covariates (e.g., sex, substance dependence) on all test items and on the latent symptom severity dimension, within each scale. Both scales: 1) contained several items that provided little or no psychometric information, 2) were inefficient, in that the majority of item response categories did not provide incremental psychometric information, 3) poorly measured participants outside of a narrow band of severity, 4) evidenced DIF for nearly all items, suggesting that item responses were, in part, determined by factors other than symptom severity. Limited to outpatients; DIF analysis only sensitive to certain forms of DIF. The present study provides evidence for significant measurement problems involving the YMRS and MADRS. More work is needed to refine these measures and/or develop suitable alternative measures of BD symptomatology for clinical trials research. Copyright © 2016 Elsevier B.V. All rights reserved.
Jin, Xiaoyan; Qian, Zhaosheng; Lu, Bangmei; Yang, Wenjing; Bi, Shuping
2011-01-01
Density functional theory (DFT) calculation is carried out to investigate the structures, (19)F and (27)Al NMR chemical shifts of aqueous Al-F complexes and their water-exchange reactions. The following investigations are performed in this paper: (1) the microscopic properties of typical aqueous Al-F complexes are obtained at the level of B3LYP/6-311+G**. Al-OH(2) bond lengths increase with F(-) replacing inner-sphere H(2)O progressively, indicating labilizing effect of F(-) ligand. The Al-OH(2) distance trans to fluoride is longer than other Al-OH(2) distance, accounting for trans effect of F(-) ligand. (19)F and (27)Al NMR chemical shifts are calculated using GIAO method at the HF/6-311+G** level relative to F(H(2)O)(6)(-) and Al(H(2)O)(6)(3+) references, respectively. The results are consistent with available experimental values; (2) the dissociative (D) activated mechanism is observed by modeling water-exchange reaction for [Al(H(2)O)(6-i)F(i)]((3-i)+) (i = 1-4). The activation energy barriers are found to decrease with increasing F(-) substitution, which is in line with experimental rate constants (k(ex)). The log k(ex) of AlF(3)(H(2)O)(3)(0) and AlF(4)(H(2)O)(2)(-) are predicted by three ways. The results indicate that the correlation between log k(ex) and Al-O bond length as well as the given transmission coefficient allows experimental rate constants to be predicted, whereas the correlation between log k(ex) and activation free energy is poor; (3) the environmental significance of this work is elucidated by the extension toward three fields, that is, polyaluminum system, monomer Al-organic system and other metal ions system with high charge-to-radius ratio.
Fossati, Andrea; Widiger, Thomas A; Borroni, Serena; Maffei, Cesare; Somma, Antonella
2017-06-01
To extend the evidence on the reliability and construct validity of the Five-Factor Model Rating Form (FFMRF) in its self-report version, two independent samples of Italian participants, which were composed of 510 adolescent high school students and 457 community-dwelling adults, respectively, were administered the FFMRF in its Italian translation. Adolescent participants were also administered the Italian translation of the Borderline Personality Features Scale for Children-11 (BPFSC-11), whereas adult participants were administered the Italian translation of the Triarchic Psychopathy Measure (TriPM). Cronbach α values were consistent with previous findings; in both samples, average interitem r values indicated acceptable internal consistency for all FFMRF scales. A multidimensional graded item response theory model indicated that the majority of FFMRF items had adequate discrimination parameters; information indices supported the reliability of the FFMRF scales. Both categorical (i.e., item-level) and scale-level regression analyses suggested that the FFMRF scores may predict a nonnegligible amount of variance in the BPFSC-11 total score in adolescent participants, and in the TriPM scale scores in adult participants.
Grajales Gonzalez, Edwing Javier
2018-01-01
and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both
Lannan, Ford M; Mamajanov, Irena; Hud, Nicholas V
2012-09-19
Structures formed by human telomere sequence (HTS) DNA are of interest due to the implication of telomeres in the aging process and cancer. We present studies of HTS DNA folding in an anhydrous, high viscosity deep eutectic solvent (DES) comprised of choline choride and urea. In this solvent, the HTS DNA forms a G-quadruplex with the parallel-stranded ("propeller") fold, consistent with observations that reduced water activity favors the parallel fold, whereas alternative folds are favored at high water activity. Surprisingly, adoption of the parallel structure by HTS DNA in the DES, after thermal denaturation and quick cooling to room temperature, requires several months, as opposed to less than 2 min in an aqueous solution. This extended folding time in the DES is, in part, due to HTS DNA becoming kinetically trapped in a folded state that is apparently not accessed in lower viscosity solvents. A comparison of times required for the G-quadruplex to convert from its aqueous-preferred folded state to its parallel fold also reveals a dependence on solvent viscosity that is consistent with Kramers rate theory, which predicts that diffusion-controlled transitions will slow proportionally with solvent friction. These results provide an enhanced view of a G-quadruplex folding funnel and highlight the necessity to consider solvent viscosity in studies of G-quadruplex formation in vitro and in vivo. Additionally, the solvents and analyses presented here should prove valuable for understanding the folding of many other nucleic acids and potentially have applications in DNA-based nanotechnology where time-dependent structures are desired.
Mondal, Bhaskar; Neese, Frank; Ye, Shengfa
2015-08-03
The development of efficient catalysts with base metals for CO2 hydrogenation has always been a major thrust of interest. A series of experimental and theoretical work has revealed that the catalytic cycle typically involves two key steps, namely, base-promoted heterolytic H2 splitting and hydride transfer to CO2, either of which can be the rate-determining step (RDS) of the entire reaction. To explore the determining factor for the nature of RDS, we present herein a comparative mechanistic investigation on CO2 hydrogenation mediated by [M(H)(η(2)-H2)(PP3(Ph))](n+) (M = Fe(II), Ru(II), and Co(III); PP3(Ph) = tris(2-(diphenylphosphino)phenyl)phosphine) type complexes. In order to construct reliable free energy profiles, we used highly correlated wave function based ab initio methods of the coupled cluster type alongside the standard density functional theory. Our calculations demonstrate that the hydricity of the metal-hydride intermediate generated by H2 splitting dictates the nature of the RDS for the Fe(II) and Co(III) systems, while the RDS for the Ru(II) catalyst appears to be ambiguous. CO2 hydrogenation catalyzed by the Fe(II) complex that possesses moderate hydricity traverses an H2-splitting RDS, whereas the RDS for the high-hydricity Co(III) species is found to be the hydride transfer. Thus, our findings suggest that hydricity can be used as a practical guide in future catalyst design. Enhancing the electron-accepting ability of low-hydricity catalysts is likely to improve their catalytic performance, while increasing the electron-donating ability of high-hydricity complexes may speed up CO2 conversion. Moreover, we also established the active roles of base NEt3 in directing the heterolytic H2 splitting and assisting product release through the formation of an acid-base complex.
Generalizability theory and item response theory
Glas, Cornelis A.W.; Eggen, T.J.H.M.; Veldkamp, B.P.
2012-01-01
Item response theory is usually applied to items with a selected-response format, such as multiple choice items, whereas generalizability theory is usually applied to constructed-response tasks assessed by raters. However, in many situations, raters may use rating scales consisting of items with a selected-response format. This chapter presents a short overview of how item response theory and generalizability theory were integrated to model such assessments. Further, the precision of the esti...
Hashiguchi, Koichi
2014-01-01
This book was written to serve as the standard textbook of elastoplasticity for students, engineers and researchers in the field of applied mechanics. The present second edition is improved thoroughly from the first edition by selecting the standard theories from various formulations and models, which are required to study the essentials of elastoplasticity steadily and effectively and will remain universally in the history of elastoplasticity. It opens with an explanation of vector-tensor analysis and continuum mechanics as a foundation to study elastoplasticity theory, extending over various strain and stress tensors and their rates. Subsequently, constitutive equations of elastoplastic and viscoplastic deformations for monotonic, cyclic and non-proportional loading behavior in a general rate and their applications to metals and soils are described in detail, and constitutive equations of friction behavior between solids and its application to the prediction of stick-slip phenomena are delineated. In additi...
Computing decay rates for new physics theories with FeynRules and MadGraph 5 _aMC@NLO
Alwall, Johan; Fuks, Benjamin; Mattelaer, Olivier; Öztürk, Deniz Gizem; Shen, Chia-Hsien
2015-01-01
We present new features of the FeynRules and MadGraph5/aMC@NLO programs for the automatic computation of decay widths that consistently include channels of arbitrary final-state multiplicity. The implementations are generic enough so that they can be used in the framework of any quantum field theory, possibly including higher-dimensional operators. We extend at the same time the conventions of the Universal FeynRules Output (or UFO) format to include decay tables and information on the total widths. We finally provide a set of representative examples of the usage of the new functions of the different codes in the framework of the Standard Model, the Higgs Effective Field Theory, the Strongly Interacting Light Higgs model and the Minimal Supersymmetric Standard Model and compare the results to available literature and programs for validation purposes.
Energy Technology Data Exchange (ETDEWEB)
Jambon, C
1962-07-01
After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [French] Apres une analyse bibliographique des causes probables d'effets isotopiques et leur comparaison, avec les simplifications qu'apporte le modele athermique, on a entrepris l'etude de la discussion isotopique du deuterium dans des molecules organiques en termes d'influences structurelles, cherchant a degager le role important de la longueur de la liaison C-D plus courte que C-H, et du rayon de Van der Waals de l'atome de D plus petit que celui de H. On a effectue des mesures cinetiques sur quelques reactions invoquant les mecanismes envisages: ionisations unimoleculaires et concentrees d'halogenes. Les modeles structuraux choisis sont: chloro 2 - cyclohexanols cis et trans H 1 et D 1; chloro 2 - cyclopentanols cis et trans H 1 et D 1; phenyl 1 - chloro 1 - propanol 2 threo H 2 et D 2. (auteur)
Energy Technology Data Exchange (ETDEWEB)
Jambon, C
1962-07-01
After a bibliographic analysis of the probable causes of isotopic effects and their comparison, with the simplifications provided by the athermal model, a discussion of the isotopic effect of deuterium in organic molecules in terms of structural influences is presented, showing the important role of the C-D bond length which is shorter than the C-H bond length, and of the D atom's Van der Waals radius, shorter than that of the H atom. Kinetic measurements were carried out on some reactions involving the mechanisms proposed: unimolecular ionizations and halogen concentrates. The structural models chosen are: 2-chloro-cyclo-hexanols cis and trans 1-H and 2-D; 2-chloro-cyclo-pentanols cis trans 1-H and 1-D; 1-phenyl-l-chloro-2-propanol threo 2-H and 2-D. (author) [French] Apres une analyse bibliographique des causes probables d'effets isotopiques et leur comparaison, avec les simplifications qu'apporte le modele athermique, on a entrepris l'etude de la discussion isotopique du deuterium dans des molecules organiques en termes d'influences structurelles, cherchant a degager le role important de la longueur de la liaison C-D plus courte que C-H, et du rayon de Van der Waals de l'atome de D plus petit que celui de H. On a effectue des mesures cinetiques sur quelques reactions invoquant les mecanismes envisages: ionisations unimoleculaires et concentrees d'halogenes. Les modeles structuraux choisis sont: chloro 2 - cyclohexanols cis et trans H 1 et D 1; chloro 2 - cyclopentanols cis et trans H 1 et D 1; phenyl 1 - chloro 1 - propanol 2 threo H 2 et D 2. (auteur)
Vogel, M.; Hansen, K.; Herlert, A.; Schweikhard, L.; Walther, C.
2002-06-01
Time-resolved photodissociation measurements of the sequential reaction Au8+CH3OH→Au8+→Au7+ and the direct reaction Au8+→Au7+ have been performed for several excitation energies. The production rates and yields of the final state Au7+ in the sequential process are strongly influenced by the excitation energy deposited into the evaporated methanol molecule during the initial fragmentation step. Both the rate constants and yields can be fitted with a single parameter, the cluster-methanol binding energy.
Generalizability theory and item response theory
Glas, Cornelis A.W.; Eggen, T.J.H.M.; Veldkamp, B.P.
2012-01-01
Item response theory is usually applied to items with a selected-response format, such as multiple choice items, whereas generalizability theory is usually applied to constructed-response tasks assessed by raters. However, in many situations, raters may use rating scales consisting of items with a
Energy Technology Data Exchange (ETDEWEB)
Chang, Tsun-Mei [Department of Chemistry, University of Wisconsin–Parkside, Kenosha, Wisconsin 53141, USA; Dang, Liem X. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 93352, USA
2017-10-28
Using our polarizable force-field models and employing classical rate theories of chemical reactions, we examine the ethylene carbonate (EC) exchange process between the first and second solvation shells around Li+ and the dissociation kinetics of ion pairs Li+-[BF4] and Li+-[PF6] in this solvent. We calculate the exchange rates using transition state theory and correct them with transmission coefficients computed by the reactive flux; Impey, Madden, and McDonald approaches; and Grote-Hynes theory. We found the residence times of EC around Li+ ions varied from 70 to 450 ps, depending on the correction method used. We found the relaxation times changed significantly from Li+-[BF4] to Li+-[PF6] ion pairs in EC. Our results also show that, in addition to affecting the free energy of dissociation in EC, the anion type also significantly influence the dissociation kinetics of ion pairing. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.
Farazdaghi, Hadi
2011-02-01
Photosynthesis is the origin of oxygenic life on the planet, and its models are the core of all models of plant biology, agriculture, environmental quality and global climate change. A theory is presented here, based on single process biochemical reactions of Rubisco, recognizing that: In the light, Rubisco activase helps separate Rubisco from the stored ribulose-1,5-bisphosphate (RuBP), activates Rubisco with carbamylation and addition of Mg²(+), and then produces two products, in two steps: (Step 1) Reaction of Rubisco with RuBP produces a Rubisco-enediol complex, which is the carboxylase-oxygenase enzyme (Enco) and (Step 2) Enco captures CO₂ and/or O₂ and produces intermediate products leading to production and release of 3-phosphoglycerate (PGA) and Rubisco. PGA interactively controls (1) the carboxylation-oxygenation, (2) electron transport, and (3) triosephosphate pathway of the Calvin-Benson cycle that leads to the release of glucose and regeneration of RuBP. Initially, the total enzyme participates in the two steps of the reaction transitionally and its rate follows Michaelis-Menten kinetics. But, for a continuous steady state, Rubisco must be divided into two concurrently active segments for the two steps. This causes a deviation of the steady state from the transitional rate. Kinetic models are developed that integrate the transitional and the steady state reactions. They are tested and successfully validated with verifiable experimental data. The single-process theory is compared to the widely used two-process theory of Farquhar et al. (1980. Planta 149, 78-90), which assumes that the carboxylation rate is either Rubisco-limited at low CO₂ levels such as CO₂ compensation point, or RuBP regeneration-limited at high CO₂. Since the photosynthesis rate cannot increase beyond the two-process theory's Rubisco limit at the CO₂ compensation point, net photosynthesis cannot increase above zero in daylight, and since there is always respiration at
Energy Technology Data Exchange (ETDEWEB)
Debreczeny, Martin Paul [Univ. of California, Berkeley, CA (United States)
1994-05-01
We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.
Casper, Patricia A.; Kantowitz, Barry H.
1988-01-01
Multiple approaches are necessary for understanding and measuring workload. In particular, physiological systems identifiable by employing cardiac measures are related to cognitive systems. One issue of debate in measuring cardiac output is the grain of analysis used in recording and summarizing data. Various experiments are reviewed, the majority of which were directed at supporting or contradicting Lacey's intake-rejection hypothesis. Two of the experiments observed heart rate in operational environments and found virtually no changes associated with mental load. The major problems facing researchers using heart rate variability, or sinus arrhthmia, as a dependent measure have been associated with valid and sensitive scoring and preventing contamination of observed results by influences unrelated to cognition. Spectral analysis of heart rate variability offers two useful procedures: analysis from the time domain and analysis from the frequency domain. Most recently, data have been collected in a divided attention experiment, the performance measures and cardiac measures of which are detailed.
Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M
2013-03-15
The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.
Dilmac, Oguz
2016-01-01
The purpose of this study is to examine the effect that using active learning techniques during museum and gallery visits has on teacher candidates' academic success rates in and attitudes toward their Visual Arts Course. In this study, the importance and requirement of education to take place in museums and art galleries is emphasized. The…
Lussier, P.; van den Berg, C.; Bijleveld, C.; Hendriks, J.
2012-01-01
The current study investigates the offending trajectories of juvenile sex offenders (JSOs) across and beyond adolescence. In doing so, the study examines the number, the rate, and the shape of nonsexual and sexual offending trajectories in a sample of JSOs followed retrospectively and prospectively
Lussier, P; van den Berg, C.J.W.; Bijleveld, C.C.J.H.; Hendriks, J.
2012-01-01
The current study investigates the offending trajectories of juvenile sex offenders (JSOs) across and beyond adolescence. In doing so, the study examines the number, the rate, and the shape of nonsexual and sexual offending trajectories in a sample of JSOs followed retrospectively and prospectively
Duncan, Juliana R; Solaka, Sarah A; Setser, D W; Holmes, Bert E
2010-01-21
The recombination of CH(2)Cl and CH(2)F radicals generates vibrationally excited CH(2)ClCH(2)Cl, CH(2)FCH(2)F, and CH(2)ClCH(2)F molecules with about 90 kcal mol(-1) of energy in a room temperature bath gas. New experimental data for CH(2)ClCH(2)F have been obtained that are combined with previously published studies for C(2)H(4)Cl(2) and C(2)H(4)F(2) to define reliable rate constants of 3.0 x 10(8) (C(2)H(4)F(2)), 2.4 x 10(8) (C(2)H(4)Cl(2)), and 1.9 x 10(8) (CH(2)ClCH(2)F) s(-1) for HCl and HF elimination. The product branching ratio for CH(2)ClCH(2)F is approximately 1. These experimental rate constants are compared to calculated statistical rate constants (RRKM) to assign threshold energies for HF and HCl elimination. The calculated rate constants are based on transition-state models obtained from calculations of electronic structures; the energy levels of the asymmetric, hindered, internal rotation were directly included in the state counting to obtain a more realistic measure for the density of internal states for the molecules. The assigned threshold energies for C(2)H(4)F(2) and C(2)H(4)Cl(2) are both 63 +/- 2 kcal mol(-1). The threshold energies for CH(2)ClCH(2)F are 65 +/- 2 (HCl) and 63 +/- 2 (HF) kcal mol(-1). These threshold energies are 5-7 kcal mol(-1) higher than the corresponding values for C(2)H(5)Cl or C(2)H(5)F, and beta-substitution of F or Cl atoms raises threshold energies for HF or HCl elimination reactions. The treatment presented here for obtaining the densities of states and the entropy of activation from models with asymmetric internal rotations with high barriers can be used to judge the validity of using a symmetric internal-rotor approximation for other cases. Finally, threshold energies for the 1,2-fluorochloroethanes are compared to those of the 1,1-fluorochloroethanes to illustrate substituent effects on the relative energies of the isomeric transition states.
International Nuclear Information System (INIS)
Di, H. J.; Cameron, K. C.; McLaren, R. G.
2000-01-01
The rates at which nutrients are released to, and removed from, the mineral nutrient pool are important in regulating the nutrient supply to plants. These nutrient transformation rates need to be taken into account when developing nutrient management strategies for economical and sustainable production. A method that is gaining popularity for determining the gross transformation rates of nutrients in the soil is the isotopic dilution technique. The technique involves labelling a soil mineral nutrient pool, e.g. NH 4 + , NO 3 - , PO 4 3- , or SO 4 2- , and monitoring the changes with time of the size of the labelled nutrient pool and the excess tracer abundance (atom %, if stable isotope tracer is used) or specific activity (if radioisotope is used) in the nutrient pool. Because of the complexity of the concepts and procedures involved, the method has sometimes been used incorrectly, and results misinterpreted. This paper discusses the isotopic dilution technique, including the theoretical background, the methodologies to determine the gross flux rates of nitrogen, phosphorus, and sulfur, and the limitations of the technique. The assumptions, conceptual models, experimental procedures, and compounding factors are discussed. Possible effects on the results by factors such as the uniformity of tracer distribution in the soil, changes in soil moisture content, substrate concentration, and aeration status, and duration of the experiment are also discussed. The influx and out-flux transformation rates derived from this technique are often contributed by several processes simultaneously, and thus cannot always be attributed to a particular nutrient transformation process. Despite the various constraints or possible compounding factors, the technique is a valuable tool that can provide important quantitative information on nutrient dynamics in the soil-plant system. Copyright (2000) CSIRO Publishing
International Nuclear Information System (INIS)
Cerjan, C.J.; Shi, S.; Miller, W.H.
1982-01-01
A simple but often reasonably accurate dynamical model--a synthesis of the semiclassical perturbation (SCP) approximation of Miller and Smith and the infinite order sudden (IOS) approximation--has been shown previously to take an exceptionally simple form when applied to the reaction path Hamiltonian derived by Miller, Handy, and Adams. This paper shows how this combined SCP-IOS reaction path model can be used to provide a simple but comprehensive description of a variety of phenomena in the dynamics of polyatomic molecules
Variational Transition State Theory
Energy Technology Data Exchange (ETDEWEB)
Truhlar, Donald G. [Univ. of Minnesota, Minneapolis, MN (United States)
2016-09-29
This is the final report on a project involving the development and applications of variational transition state theory. This project involved the development of variational transition state theory for gas-phase reactions, including optimized multidimensional tunneling contributions and the application of this theory to gas-phase reactions with a special emphasis on developing reaction rate theory in directions that are important for applications to combustion. The development of variational transition state theory with optimized multidimensional tunneling as a useful computational tool for combustion kinetics involved eight objectives.
Seyrich, Maximilian; Sornette, Didier
2016-04-01
We present a plausible micro-founded model for the previously postulated power law finite time singular form of the crash hazard rate in the Johansen-Ledoit-Sornette (JLS) model of rational expectation bubbles. The model is based on a percolation picture of the network of traders and the concept that clusters of connected traders share the same opinion. The key ingredient is the notion that a shift of position from buyer to seller of a sufficiently large group of traders can trigger a crash. This provides a formula to estimate the crash hazard rate by summation over percolation clusters above a minimum size of a power sa (with a>1) of the cluster sizes s, similarly to a generalized percolation susceptibility. The power sa of cluster sizes emerges from the super-linear dependence of group activity as a function of group size, previously documented in the literature. The crash hazard rate exhibits explosive finite time singular behaviors when the control parameter (fraction of occupied sites, or density of traders in the network) approaches the percolation threshold pc. Realistic dynamics are generated by modeling the density of traders on the percolation network by an Ornstein-Uhlenbeck process, whose memory controls the spontaneous excursion of the control parameter close to the critical region of bubble formation. Our numerical simulations recover the main stylized properties of the JLS model with intermittent explosive super-exponential bubbles interrupted by crashes.
DEFF Research Database (Denmark)
Wæver, Ole
2009-01-01
-empiricism and anti-positivism of his position. Followers and critics alike have treated Waltzian neorealism as if it was at bottom a formal proposition about cause-effect relations. The extreme case of Waltz being so victorious in the discipline, and yet being consistently mis-interpreted on the question of theory......, shows the power of a dominant philosophy of science in US IR, and thus the challenge facing any ambitious theorising. The article suggests a possible movement of fronts away from the ‘fourth debate' between rationalism and reflectivism towards one of theory against empiricism. To help this new agenda...
Saltiel, J; Dmitrenko, O; Pillai, Z S; Klima, R; Wang, S; Wharton, T; Huang, Z-N; van de Burgt, L J; Arranz, J
2008-05-01
Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O(2), lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt --> ct direction, as had been observed for the ct --> tt direction, and suggesting an energy minimum at the (3)ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (k(d)) from twisted geometries. Starting from cc-DPB, varphi(cc-->tt) increases with increasing [cc-DPB] whereas varphi(cc-->ct) is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental DeltaH between (3)tt-DPB* and (3)tp-DPB*, 2.7 kcal mol(-1), is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated DeltaS = 4.04 eu between the two triplets gives k(d) = (2.4-6.4) x 10(7) s(-1), close to 1.70 x 10(7) s(-1), the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.
Loerting, Thomas; Liedl, Klaus R.
2000-01-01
The hydration rate constant of sulfur trioxide to sulfuric acid is shown to depend sensitively on water vapor pressure. In the 1:1 SO3-H2O complex, the rate is predicted to be slower by about 25 orders of magnitude compared with laboratory results [Lovejoy, E. R., Hanson, D. R. & Huey, L. G. (1996) J. Phys. Chem. 100, 19911–19916; Jayne, J. T., Pöschl, U., Chen, Y.-m., Dai, D., Molina, L. T., Worsnop, D. R., Kolb, C. E. & Molina, M. J. (1997) J. Phys. Chem. A 101, 10000–10011]. This discrepancy is removed mostly by allowing a second and third water molecule to participate. An asynchronous water-mediated double proton transfer concerted with the nucleophilic attack and a double proton transfer accompanied by a transient H3O+ rotation are predicted to be the fastest reaction mechanisms. Comparison of the predicted negative apparent “activation” energies with the experimental finding indicates that in our atmosphere, different reaction paths involving two and three water molecules are taken in the process of forming sulfate aerosols and consequently acid rain. PMID:10922048
Nonlinear closure relations theory for transport processes in nonequilibrium systems
International Nuclear Information System (INIS)
Sonnino, Giorgio
2009-01-01
A decade ago, a macroscopic theory for closure relations has been proposed for systems out of Onsager's region. This theory is referred to as the thermodynamic field theory (TFT). The aim of this work was to determine the nonlinear flux-force relations that respect the thermodynamic theorems for systems far from equilibrium. We propose a formulation of the TFT where one of the basic restrictions, namely, the closed-form solution for the skew-symmetric piece of the transport coefficients, has been removed. In addition, the general covariance principle is replaced by the De Donder-Prigogine thermodynamic covariance principle (TCP). The introduction of TCP requires the application of an appropriate mathematical formalism, which is referred to as the entropy-covariant formalism. By geometrical arguments, we prove the validity of the Glansdorff-Prigogine universal criterion of evolution. A new set of closure equations determining the nonlinear corrections to the linear ('Onsager') transport coefficients is also derived. The geometry of the thermodynamic space is non-Riemannian. However, it tends to be Riemannian for high values of the entropy production. In this limit, we recover the transport equations found by the old theory. Applications of our approach to transport in magnetically confined plasmas, materials submitted to temperature, and electric potential gradients or to unimolecular triangular chemical reactions can be found at references cited herein. Transport processes in tokamak plasmas are of particular interest. In this case, even in the absence of turbulence, the state of the plasma remains close to (but, it is not in) a state of local equilibrium. This prevents the transport relations from being linear.
International Nuclear Information System (INIS)
Bostick, W.D.; McCulla, W.H.; Trowbridge, L.D.
1987-04-01
In the gas-phase, uranium hexafluoride decomposes thermally in a quasi-unimolecular reaction to yield uranium pentafluoride and atomic fluorine. We have investigated this reaction using the relatively new technique of laser-powered homogeneous pyrolysis, in which a megawatt infrared laser is used to generate short pulses of high gas temperatures under strictly homogeneous conditions. In our investigation, SiF 4 is used as the sensitizer to absorb energy from a pulsed CO 2 laser and to transfer this energy by collisions with the reactant gas. Ethyl chloride is used as an external standard ''thermometer'' gas to permit estimation of the unimolecular reaction rate constants by a relative rate approach. When UF 6 is the reactant, CF 3 Cl is used as reagent to trap atomic fluorine reaction product, forming CF 4 as a stable indicator which is easily detected by infrared spectroscopy. Using these techniques, we estimate the UF 6 unimolecular reaction rate constant near the high-pressure limit. In the Appendix, we describe a computer program, written for the IBM PC, which predicts unimolecular rate constants based on the Rice-Ramsperger-Kassel theory. Parameterization of the theoretical model is discussed, and recommendations are made for ''appropriate'' input parameters for use in predicting the gas-phase unimolecular reaction rate for UF 6 as a function of temperature and gas composition and total pressure. 85 refs., 17 figs., 14 tabs
Coopersmith, Michael
2011-01-01
A relation between interest rates and inflation is presented using a two component economic model and a simple general principle. Preliminary results indicate a remarkable similarity to classical economic theories, in particular that of Wicksell.
International Nuclear Information System (INIS)
Markland, J.T.
1992-01-01
Techniques used in conventional project appraisal are mathematically very simple in comparison to those used in reservoir modelling, and in the geosciences. Clearly it would be possible to value assets in mathematically more sophisticated ways if it were meaningful and worthwhile so to do. The DCf approach in common use has recognized limitations; the inability to select a meaningful discount rate being particularly significant. Financial Theory has advanced enormously over the last few years, along with computational techniques, and methods are beginning to appear which may change the way we do project evaluations in practice. The starting point for all of this was a paper by Black and Scholes, which asserts that almost all corporate liabilities can be viewed as options of varying degrees of complexity. Although the financial presentation may be unfamiliar to engineers and geoscientists, some of the concepts used will not be. This paper outlines, in plain English, the basis of option pricing theory for assessing the market value of a project. it also attempts to assess the future role of this type of approach in practical Petroleum Exploration and Engineering economics. Reference is made to relevant published Natural Resource literature
Jara, Pascual; Torrecillas, Blas
1988-01-01
The papers in this proceedings volume are selected research papers in different areas of ring theory, including graded rings, differential operator rings, K-theory of noetherian rings, torsion theory, regular rings, cohomology of algebras, local cohomology of noncommutative rings. The book will be important for mathematicians active in research in ring theory.
DEFF Research Database (Denmark)
Hendricks, Vincent F.
Game Theory is a collection of short interviews based on 5 questions presented to some of the most influential and prominent scholars in game theory. We hear their views on game theory, its aim, scope, use, the future direction of game theory and how their work fits in these respects....
An Exciting Aspect of Nanotechnology: Unimolecular Electronics
Directory of Open Access Journals (Sweden)
Metzger R. M.
2013-08-01
Full Text Available This is a brief update on our experimental work towards better one-molecule-thick monolayer rectifiers of electrical current, and on theoretical progress towards a one-molecule amplifier of electrical current. This program aims to provide electronic devices at the 2 to 3 nm level, as a dramatic advance towards practical integrated circuits of the future.
Unimolecular Reactions of Nitrites and Nitrates.
1983-04-01
verified the mechanism as being the one originally proposed by Levy, RONO - RO + NO RO + NO- 1 2*RONO •I kRO + NO-- ROH HHO -Hi k5 :and not by direct...produced by ,’Levy’s mechanism. I1 Emission from CH30, C2H50, and l-C3H70 radicals were observed in the photolysis of these nitrites between...wavelengths of 2000 and 1100 A, by Ohbayashi, Akimoto and Tanaka [78]. Emission was assigned to the (A2A1IX2E) transition of CH30 . Bands of NO were also *i
International Nuclear Information System (INIS)
Chan Hongmo.
1987-10-01
The paper traces the development of the String Theory, and was presented at Professor Sir Rudolf Peierls' 80sup(th) Birthday Symposium. The String theory is discussed with respect to the interaction of strings, the inclusion of both gauge theory and gravitation, inconsistencies in the theory, and the role of space-time. The physical principles underlying string theory are also outlined. (U.K.)
Children's theories of motivation.
Gurland, Suzanne T; Glowacky, Victoria C
2011-09-01
To investigate children's theories of motivation, we asked 166 children (8-12 years of age) to rate the effect of various motivational strategies on task interest, over the short and long terms, in activities described as appealing or unappealing. Children viewed the rewards strategy as resulting in greatest interest except when implemented over the long term for appealing activities. Individual difference analyses revealed that some children held operant theories of motivation, in which rewards were central, and others held hybrid theories, in which rewards were key, but some allowance was made for interest to be self-sustaining in the absence of inducements. Children's theories predicted their academic self-regulation. Their theories are discussed relative to an expert theory of motivation. Copyright © 2011 Elsevier Inc. All rights reserved.
Liyanage, Rohana; Devarapalli, Nagarjuna; Pyland, Derek B; Puckett, Latisha M; Phan, N H; Starch, Joel A; Okimoto, Mark R; Gidden, Jennifer; Stites, Wesley E; Lay, Jackson O
2012-12-15
Protein equilibrium snapshot by hydrogen/deuterium exchange electrospray ionization mass spectrometry (PEPS-HDX-ESI-MS or PEPS) is a method recently introduced for estimating protein folding energies and rates. Herein we describe the basis for this method using both theory and new experiments. Benchmark experiments were conducted using ubiquitin because of the availability of reference data for folding and unfolding rates from NMR studies. A second set of experiments was also conducted to illustrate the surprising resilience of the PEPS to changes in HDX time, using staphylococcal nuclease and time frames ranging from a few seconds to several minutes. Theory suggests that PEPS experiments should be conducted at relatively high denaturant concentrations, where the protein folding/unfolding rates are slow with respect to HDX and the life times of both the closed and open states are long enough to be sampled experimentally. Upon deliberate denaturation, changes in folding/unfolding are correlated with associated changes in the ESI-MS signal upon fast HDX. When experiments are done quickly, typically within a few seconds, ESI-MS signals, corresponding to the equilibrium population of the native (closed) and denatured (open) states can both be detected. The interior of folded proteins remains largely un-exchanged. Amongst MS methods, the simultaneous detection of both states in the spectrum is unique to PEPS and provides a "snapshot" of these populations. The associated ion intensities are used to estimate the protein folding equilibrium constant (or the free energy change, ΔG). Linear extrapolation method (LEM) plots of derived ΔG values for each denaturant concentration can then be used to calculate ΔG in the absence of denaturant, ΔG(H(2)O). In accordance with the requirement for detection of signals for both the folded and unfolded states, this theoretical framework predicts that PEPS experiments work best at the middle of the denaturation curve where natured
String theory or field theory?
International Nuclear Information System (INIS)
Marshakov, A.V.
2002-01-01
The status of string theory is reviewed, and major recent developments - especially those in going beyond perturbation theory in the string theory and quantum field theory frameworks - are analyzed. This analysis helps better understand the role and place of experimental phenomena, it is emphasized that there are some insurmountable problems inherent in it - notably the impossibility to formulate the quantum theory of gravity on its basis - which prevent it from being a fundamental physical theory of the world of microscopic distances. It is this task, the creation of such a theory, which string theory, currently far from completion, is expected to solve. In spite of its somewhat vague current form, string theory has already led to a number of serious results and greatly contributed to progress in the understanding of quantum field theory. It is these developments, which are our concern in this review [ru
International Nuclear Information System (INIS)
Uehara, S.
1985-01-01
Of all supergravity theories, the maximal, i.e., N = 8 in 4-dimension or N = 1 in 11-dimension, theory should perform the unification since it owns the highest degree of symmetry. As to the N = 1 in d = 11 theory, it has been investigated how to compactify to the d = 4 theories. From the phenomenological point of view, local SUSY GUTs, i.e., N = 1 SUSY GUTs with soft breaking terms, have been studied from various angles. The structures of extended supergravity theories are less understood than those of N = 1 supergravity theories, and matter couplings in N = 2 extended supergravity theories are under investigation. The harmonic superspace was recently proposed which may be useful to investigate the quantum effects of extended supersymmetry and supergravity theories. As to the so-called Kaluza-Klein supergravity, there is another possibility. (Mori, K.)
Johnstone, PT
2014-01-01
Focusing on topos theory's integration of geometric and logical ideas into the foundations of mathematics and theoretical computer science, this volume explores internal category theory, topologies and sheaves, geometric morphisms, other subjects. 1977 edition.
Dorogovtsev, A Ya; Skorokhod, A V; Silvestrov, D S; Skorokhod, A V
1997-01-01
This book of problems is intended for students in pure and applied mathematics. There are problems in traditional areas of probability theory and problems in the theory of stochastic processes, which has wide applications in the theory of automatic control, queuing and reliability theories, and in many other modern science and engineering fields. Answers to most of the problems are given, and the book provides hints and solutions for more complicated problems.
International Nuclear Information System (INIS)
Lee, B.W.
1976-01-01
Some introductory remarks to Yang-Mills fields are given and the problem of the Coulomb gauge is considered. The perturbation expansion for quantized gauge theories is discussed and a survey of renormalization schemes is made. The role of Ward-Takahashi identities in gauge theories is discussed. The author then discusses the renormalization of pure gauge theories and theories with spontaneously broken symmetry. (B.R.H.)
Methods of thermal field theory
Energy Technology Data Exchange (ETDEWEB)
Mallik, S [Saha Institute of Nuclear Physics, Calcutta (India)
1998-11-01
We introduce the basic ideas of thermal field theory and review its path integral formulation. We then discuss the problems of QCD theory at high and at low temperatures. At high temperature the naive perturbation expansion breaks down and is cured by resummation. We illustrate this improved perturbation expansion with the g{sup 2}{phi}{sup 4} theory and then sketch its application to find the gluon damping rate in QCD theory. At low temperature the hadronic phase is described systematically by the chiral perturbation theory. The results obtained from this theory for the quark and the gluon condensates are discussed. (author) 22 refs., 6 figs.
Directory of Open Access Journals (Sweden)
Juan David Gómez C.
2008-12-01
Full Text Available The current trend towards miniaturization in the microelectronics industryhas pushed for the development of theories intended to explain the behaviorof materials at small scales. In the particular case of metals, a class ofavailable non–classical continuum mechanics theories has been recently employedin order to explain the wide range of observed behavior at the micronscale. The practical use of the proposed theories remains limited due to issuesin its numerical implementation. First, in displacement–based finite elementformulations the need appears for higher orders of continuity in the interpolationshape functions in order to maintain the convergence rate upon meshrefinement. This limitation places strong restrictions in the geometries of theavailable elements. Second, the available inelastic constitutive models for smallscale applications have been cast into deformation theory formulations limitingthe set of problems to those exhibiting proportional loading only. In thisarticle two contributions are made for the particular case of a Cosserat couplestress continuum. First it describes a numerical scheme based on a penaltyfunction/reduced integration approach that allows for the proper treatment ofthe higher order terms present in Cosserat like theories. This scheme results in a new finite element that can be directly implemented into commercial finiteelement codes. Second, a flow theory of plasticity incorporating size effects isproposed for the case of rate independent materials overcoming the limitationsin the deformation theory formulations. The constitutive model and its correspondingtime–integration algorithm are coupled to the new proposed finiteelement and implemented in the form of a user element subroutine into thecommercial code ABAQUS. The validity of the approach is shown via numericalsimulations of the microbending experiment on thin Nickel foils reportedin the literature.La tendencia actual hacia la miniaturización en la
Loring, FH
2014-01-01
Summarising the most novel facts and theories which were coming into prominence at the time, particularly those which had not yet been incorporated into standard textbooks, this important work was first published in 1921. The subjects treated cover a wide range of research that was being conducted into the atom, and include Quantum Theory, the Bohr Theory, the Sommerfield extension of Bohr's work, the Octet Theory and Isotopes, as well as Ionisation Potentials and Solar Phenomena. Because much of the material of Atomic Theories lies on the boundary between experimentally verified fact and spec
Harris, Tina
2015-04-29
Grounded theory is a popular research approach in health care and the social sciences. This article provides a description of grounded theory methodology and its key components, using examples from published studies to demonstrate practical application. It aims to demystify grounded theory for novice nurse researchers, by explaining what it is, when to use it, why they would want to use it and how to use it. It should enable nurse researchers to decide if grounded theory is an appropriate approach for their research, and to determine the quality of any grounded theory research they read.
Variational transition state theory
International Nuclear Information System (INIS)
Truhlar, D.G.
1986-01-01
This project is concerned with the development and applications of generalized transition state theory and multidimensional tunneling approximations to chemical reaction rates. They have developed and implemented several practical versions of variational transition state theory (VTST), namely canonical variational theory (CVT), improved canonical variational theory (ICVT), and microcanonical variational theory (μVT). They have also developed and implemented several accurate multidimensional semiclassical tunneling approximations, the most accurate of which are the small-curvature semiclassical adiabatic (SCSA), large-curvature version-3 (LC3), and least-action (LA) approximations. They have applied the methods to thermal rate constants, using transmission coefficients based on ground-state tunneling, and they have also presented and applied adiabatic and diabatic extensions to calculated rate constants for vibrationally excited reactants. Their general goal is to develop accurate methods for calculating chemical reaction rate constants that remain practical even for reasonably complicated molecules. The approximations mentioned above yield rate constants for systems whose potential energy surface is known or assumed. Thus a second, equally important aspect of their work is the determination or modeling, semi-empirically and/or from electronic structure calculations, of potential energy surfaces
Number theory via Representation theory
Indian Academy of Sciences (India)
2014-11-09
Number theory via Representation theory. Eknath Ghate. November 9, 2014. Eightieth Annual Meeting, Chennai. Indian Academy of Sciences1. 1. This is a non-technical 20 minute talk intended for a general Academy audience.
International Nuclear Information System (INIS)
Schwarz, J.H.
1985-01-01
Dual string theories, initially developed as phenomenological models of hadrons, now appear more promising as candidates for a unified theory of fundamental interactions. Type I superstring theory (SST I), is a ten-dimensional theory of interacting open and closed strings, with one supersymmetry, that is free from ghosts and tachyons. It requires that an SO(eta) or Sp(2eta) gauge group be used. A light-cone-gauge string action with space-time supersymmetry automatically incorporates the superstring restrictions and leads to the discovery of type II superstring theory (SST II). SST II is an interacting theory of closed strings only, with two D=10 supersymmetries, that is also free from ghosts and tachyons. By taking six of the spatial dimensions to form a compact space, it becomes possible to reconcile the models with our four-dimensional perception of spacetime and to define low-energy limits in which SST I reduces to N=4, D=4 super Yang-Mills theory and SST II reduces to N=8, D=4 supergravity theory. The superstring theories can be described by a light-cone-gauge action principle based on fields that are functionals of string coordinates. With this formalism any physical quantity should be calculable. There is some evidence that, unlike any conventional field theory, the superstring theories provide perturbatively renormalizable (SST I) or finite (SST II) unifications of gravity with other interactions
String theory or field theory?
International Nuclear Information System (INIS)
Marshakov, Andrei V
2002-01-01
The status of string theory is reviewed, and major recent developments - especially those in going beyond perturbation theory in the string theory and quantum field theory frameworks - are analyzed. This analysis helps better understand the role and place of string theory in the modern picture of the physical world. Even though quantum field theory describes a wide range of experimental phenomena, it is emphasized that there are some insurmountable problems inherent in it - notably the impossibility to formulate the quantum theory of gravity on its basis - which prevent it from being a fundamental physical theory of the world of microscopic distances. It is this task, the creation of such a theory, which string theory, currently far from completion, is expected to solve. In spite of its somewhat vague current form, string theory has already led to a number of serious results and greatly contributed to progress in the understanding of quantum field theory. It is these developments which are our concern in this review. (reviews of topical problems)
Dependence theory via game theory
Grossi, D.; Turrini, P.
2011-01-01
In the multi-agent systems community, dependence theory and game theory are often presented as two alternative perspectives on the analysis of social interaction. Up till now no research has been done relating these two approaches. The unification presented provides dependence theory with the sort
The liquidity preference theory: a critical analysis
Giancarlo Bertocco; Andrea Kalajzic
2014-01-01
Keynes in the General Theory, explains the monetary nature of the interest rate by means of the liquidity preference theory. The objective of this paper is twofold. First, to point out the limits of the liquidity preference theory. Second, to present an explanation of the monetary nature of the interest rate based on the arguments with which Keynes responded to the criticism levelled at the liquidity preference theory by supporters of the loanable funds theory such as Ohlin and Robertson. It ...
Variational transition-state theory
International Nuclear Information System (INIS)
Truhlar, D.G.; Garrett, B.C.
1980-01-01
A general introduction to and some results from studies of a procedure called variational transition-state theory are presented. A fundamental assumption of this theory is that the net rate of forward reaction at equilibrium equals the equilibrium flux in the product direction through the transition state where the transition state is a surface in phase space dividing reactants from products. Classical generalized-transition-state-theory calculations for nine collinear systems are compared to classical trajectory calculations. This new technique should provide useful insight into the successes and failures of the conventional theory and useful quantitative estimates of possible errors on the predictions of conventional transition-state theory. This should also contribute to a more accurate theory now available for the practical calculations of chemical reaction rates and thermochemical and structural interpretations of rate processes
Chang, CC
2012-01-01
Model theory deals with a branch of mathematical logic showing connections between a formal language and its interpretations or models. This is the first and most successful textbook in logical model theory. Extensively updated and corrected in 1990 to accommodate developments in model theoretic methods - including classification theory and nonstandard analysis - the third edition added entirely new sections, exercises, and references. Each chapter introduces an individual method and discusses specific applications. Basic methods of constructing models include constants, elementary chains, Sko
Aubin, Jean-Pierre; Saint-Pierre, Patrick
2011-01-01
Viability theory designs and develops mathematical and algorithmic methods for investigating the adaptation to viability constraints of evolutions governed by complex systems under uncertainty that are found in many domains involving living beings, from biological evolution to economics, from environmental sciences to financial markets, from control theory and robotics to cognitive sciences. It involves interdisciplinary investigations spanning fields that have traditionally developed in isolation. The purpose of this book is to present an initiation to applications of viability theory, explai
Cox, David A
2012-01-01
Praise for the First Edition ". . .will certainly fascinate anyone interested in abstract algebra: a remarkable book!"—Monatshefte fur Mathematik Galois theory is one of the most established topics in mathematics, with historical roots that led to the development of many central concepts in modern algebra, including groups and fields. Covering classic applications of the theory, such as solvability by radicals, geometric constructions, and finite fields, Galois Theory, Second Edition delves into novel topics like Abel’s theory of Abelian equations, casus irreducibili, and the Galo
Dufwenberg, Martin
2011-03-01
Game theory is a toolkit for examining situations where decision makers influence each other. I discuss the nature of game-theoretic analysis, the history of game theory, why game theory is useful for understanding human psychology, and why game theory has played a key role in the recent explosion of interest in the field of behavioral economics. WIREs Cogni Sci 2011 2 167-173 DOI: 10.1002/wcs.119 For further resources related to this article, please visit the WIREs website. Copyright © 2010 John Wiley & Sons, Ltd.
Hashiguchi, Koichi
2009-01-01
This book details the mathematics and continuum mechanics necessary as a foundation of elastoplasticity theory. It explains physical backgrounds with illustrations and provides descriptions of detailed derivation processes..
International Nuclear Information System (INIS)
Bartlett, R.; Kirtman, B.; Davidson, E.R.
1978-01-01
After noting some advantages of using perturbation theory some of the various types are related on a chart and described, including many-body nonlinear summations, quartic force-field fit for geometry, fourth-order correlation approximations, and a survey of some recent work. Alternative initial approximations in perturbation theory are also discussed. 25 references
R. Veenhoven (Ruut)
2014-01-01
markdownabstract__Abstract__ Need theory of happiness is linked to affect theory, which holds that happiness is a reflection of how well we feel generally. In this view, we do not "calculate" happiness but rather "infer" it, the typical heuristic being "I feel good most of the time, hence
Bouwkamp, C.J.
1954-01-01
A critical review is presented of recent progress in classical diffraction theory. Both scalar and electromagnetic problems are discussed. The report may serve as an introduction to general diffraction theory although the main emphasis is on diffraction by plane obstacles. Various modifications of
Lukeš, Jaroslav; Netuka, Ivan; Veselý, Jiří
1988-01-01
Within the tradition of meetings devoted to potential theory, a conference on potential theory took place in Prague on 19-24, July 1987. The Conference was organized by the Faculty of Mathematics and Physics, Charles University, with the collaboration of the Institute of Mathematics, Czechoslovak Academy of Sciences, the Department of Mathematics, Czech University of Technology, the Union of Czechoslovak Mathematicians and Physicists, the Czechoslovak Scientific and Technical Society, and supported by IMU. During the Conference, 69 scientific communications from different branches of potential theory were presented; the majority of them are in cluded in the present volume. (Papers based on survey lectures delivered at the Conference, its program as well as a collection of problems from potential theory will appear in a special volume of the Lecture Notes Series published by Springer-Verlag). Topics of these communications truly reflect the vast scope of contemporary potential theory. Some contributions deal...
DEFF Research Database (Denmark)
Bjerg, Ole; Presskorn-Thygesen, Thomas
2017-01-01
The paper is a contribution to current debates about conspiracy theories within philosophy and cultural studies. Wittgenstein’s understanding of language is invoked to analyse the epistemological effects of designating particular questions and explanations as a ‘conspiracy theory......’. It is demonstrated how such a designation relegates these questions and explanations beyond the realm of meaningful discourse. In addition, Agamben’s concept of sovereignty is applied to explore the political effects of using the concept of conspiracy theory. The exceptional epistemological status assigned...... to alleged conspiracy theories within our prevalent paradigms of knowledge and truth is compared to the exceptional legal status assigned to individuals accused of terrorism under the War on Terror. The paper concludes by discussing the relation between conspiracy theory and ‘the paranoid style...
1999-11-08
In these lectures I will build up the concept of field theory using the language of Feynman diagrams. As a starting point, field theory in zero spacetime dimensions is used as a vehicle to develop all the necessary techniques: path integral, Feynman diagrams, Schwinger-Dyson equations, asymptotic series, effective action, renormalization etc. The theory is then extended to more dimensions, with emphasis on the combinatorial aspects of the diagrams rather than their particular mathematical structure. The concept of unitarity is used to, finally, arrive at the various Feynman rules in an actual, four-dimensional theory. The concept of gauge-invariance is developed, and the structure of a non-abelian gauge theory is discussed, again on the level of Feynman diagrams and Feynman rules.
Liu, Baoding
2015-01-01
When no samples are available to estimate a probability distribution, we have to invite some domain experts to evaluate the belief degree that each event will happen. Perhaps some people think that the belief degree should be modeled by subjective probability or fuzzy set theory. However, it is usually inappropriate because both of them may lead to counterintuitive results in this case. In order to rationally deal with belief degrees, uncertainty theory was founded in 2007 and subsequently studied by many researchers. Nowadays, uncertainty theory has become a branch of axiomatic mathematics for modeling belief degrees. This is an introductory textbook on uncertainty theory, uncertain programming, uncertain statistics, uncertain risk analysis, uncertain reliability analysis, uncertain set, uncertain logic, uncertain inference, uncertain process, uncertain calculus, and uncertain differential equation. This textbook also shows applications of uncertainty theory to scheduling, logistics, networks, data mining, c...
DEFF Research Database (Denmark)
Hjørland, Birger
2009-01-01
Concept theory is an extremely broad, interdisciplinary and complex field of research related to many deep fields with very long historical traditions without much consensus. However, information science and knowledge organization cannot avoid relating to theories of concepts. Knowledge...... organizing systems (e.g. classification systems, thesauri and ontologies) should be understood as systems basically organizing concepts and their semantic relations. The same is the case with information retrieval systems. Different theories of concepts have different implications for how to construe......, evaluate and use such systems. Based on "a post-Kuhnian view" of paradigms this paper put forward arguments that the best understanding and classification of theories of concepts is to view and classify them in accordance with epistemological theories (empiricism, rationalism, historicism and pragmatism...
Directory of Open Access Journals (Sweden)
Luis C. Orozco V.
2011-08-01
Full Text Available Introducción: A pesar del uso extendido del formulario de Zung para ansiedad no se encontraron artículos sobre la invarianza de la prueba. Objetivo: Establecer la invarianza por género del formulario para ansiedad autodiligenciado de Zung desde la Teoría Clásica. Métodos: Muestra no aleaotoria de 336 mujeres y 205 hombres estudiantes de varias universidades colombianas que diligenciaron el formulario. El análisis se realizo con análisis confimatorio de factores. Se investigó la invarianza dimensional, de configuración y métrica. Resultados: Se encontró que las invarianzas dimensional y de configuración se cumplen al demostrarse que el constructo es unidimensional en los 2 géneros, seleccionando los modelos con el Criterio de información Bayesiano y que la carga de los ítems es en general alta. No así la invarianza métrica para la cual debieron eliminarse 9 ítems para lograr invarianza en las cargas. Conclusión: El formulario de Zung presenta invarianzas dimensional, de configuración y métrica con 11 ítems. Salud UIS 2011; 43 (2: 159-166Introduction: There is not a published report of the invariance of anxiety Zung test, although is widely used. Objective: To stablish gender invariance of the Zung self-rating anxiety scale using Classical Test Theory. Methods: A non random sample of 336 women and 205 men students from several colombian universities that answered the scale. Confirmatory factor analysis was performed. Dimensional, configurational and metric invariance were investigated. Results: Dimensional and configurational invariance are met because for both genders theres is one dimension, using Bayesian Information Crietria as the model selection strategy, and the loadings are generally high. The metric invariance was obtained after deleting 9 items. Conclusion: Eleven items of The Zung self-rating anxiety scale show dimensional, configurational and metric invariance. Salud UIS 2011; 43 (2: 159-166
Children's Theories of Motivation
Gurland, Suzanne T.; Glowacky, Victoria C.
2011-01-01
To investigate children's theories of motivation, we asked 166 children (8-12 years of age) to rate the effect of various motivational strategies on task interest, over the short and long terms, in activities described as appealing or unappealing. Children viewed the rewards strategy as resulting in greatest interest except when implemented over…
Neutron resonance absorption theory
International Nuclear Information System (INIS)
Reuss, P.
1991-11-01
After some recalls on the physics of neutron resonance absorption during their slowing down, this paper presents the main features of the theoretical developments performed by the french school of reactor physics: the effective reaction rate method so called Livolant-Jeanpierre theory, the generalizations carried out by the author, and the probability table method [fr
Andrews, George E
1994-01-01
Although mathematics majors are usually conversant with number theory by the time they have completed a course in abstract algebra, other undergraduates, especially those in education and the liberal arts, often need a more basic introduction to the topic.In this book the author solves the problem of maintaining the interest of students at both levels by offering a combinatorial approach to elementary number theory. In studying number theory from such a perspective, mathematics majors are spared repetition and provided with new insights, while other students benefit from the consequent simpl
Schmidli, Hanspeter
2017-01-01
This book provides an overview of classical actuarial techniques, including material that is not readily accessible elsewhere such as the Ammeter risk model and the Markov-modulated risk model. Other topics covered include utility theory, credibility theory, claims reserving and ruin theory. The author treats both theoretical and practical aspects and also discusses links to Solvency II. Written by one of the leading experts in the field, these lecture notes serve as a valuable introduction to some of the most frequently used methods in non-life insurance. They will be of particular interest to graduate students, researchers and practitioners in insurance, finance and risk management.
DEFF Research Database (Denmark)
Smith, Shelley
This paper came about within the context of a 13-month research project, Focus Area 1 - Method and Theory, at the Center for Public Space Research at the Royal Academy of the Arts School of Architecture in Copenhagen, Denmark. This project has been funded by RealDania. The goals of the research...... project, Focus Area 1 - Method and Theory, which forms the framework for this working paper, are: * To provide a basis from which to discuss the concept of public space in a contemporary architectural and urban context - specifically relating to theory and method * To broaden the discussion of the concept...
Lubliner, Jacob
2008-01-01
The aim of Plasticity Theory is to provide a comprehensive introduction to the contemporary state of knowledge in basic plasticity theory and to its applications. It treats several areas not commonly found between the covers of a single book: the physics of plasticity, constitutive theory, dynamic plasticity, large-deformation plasticity, and numerical methods, in addition to a representative survey of problems treated by classical methods, such as elastic-plastic problems, plane plastic flow, and limit analysis; the problem discussed come from areas of interest to mechanical, structural, and
DEFF Research Database (Denmark)
Linder, Stefan; Foss, Nicolai Juul
Agency theory studies the problems and solutions linked to delegation of tasks from principals to agents in the context of conflicting interests between the parties. Beginning from clear assumptions about rationality, contracting and informational conditions, the theory addresses problems of ex...... ante (“hidden characteristics”) as well as ex post information asymmetry (“hidden action”), and examines conditions under which various kinds of incentive instruments and monitoring arrangements can be deployed to minimize the welfare loss. Its clear predictions and broad applicability have allowed...... agency theory to enjoy considerable scientific impact on social science; however, it has also attracted considerable criticism....
DEFF Research Database (Denmark)
Linder, Stefan; Foss, Nicolai Juul
2015-01-01
Agency theory studies the problems and solutions linked to delegation of tasks from principals to agents in the context of conflicting interests between the parties. Beginning from clear assumptions about rationality, contracting, and informational conditions, the theory addresses problems of ex...... ante (‘hidden characteristics’) as well as ex post information asymmetry (‘hidden action’), and examines conditions under which various kinds of incentive instruments and monitoring arrangements can be deployed to minimize the welfare loss. Its clear predictions and broad applicability have allowed...... agency theory to enjoy considerable scientific impact on social science; however, it has also attracted considerable criticism....
Nel, Louis
2016-01-01
This book presents a detailed, self-contained theory of continuous mappings. It is mainly addressed to students who have already studied these mappings in the setting of metric spaces, as well as multidimensional differential calculus. The needed background facts about sets, metric spaces and linear algebra are developed in detail, so as to provide a seamless transition between students' previous studies and new material. In view of its many novel features, this book will be of interest also to mature readers who have studied continuous mappings from the subject's classical texts and wish to become acquainted with a new approach. The theory of continuous mappings serves as infrastructure for more specialized mathematical theories like differential equations, integral equations, operator theory, dynamical systems, global analysis, topological groups, topological rings and many more. In light of the centrality of the topic, a book of this kind fits a variety of applications, especially those that contribute to ...
Hodges, Wilfrid
1993-01-01
An up-to-date and integrated introduction to model theory, designed to be used for graduate courses (for students who are familiar with first-order logic), and as a reference for more experienced logicians and mathematicians.
Lunardi, Alessandra
2018-01-01
This book is the third edition of the 1999 lecture notes of the courses on interpolation theory that the author delivered at the Scuola Normale in 1998 and 1999. In the mathematical literature there are many good books on the subject, but none of them is very elementary, and in many cases the basic principles are hidden below great generality. In this book the principles of interpolation theory are illustrated aiming at simplification rather than at generality. The abstract theory is reduced as far as possible, and many examples and applications are given, especially to operator theory and to regularity in partial differential equations. Moreover the treatment is self-contained, the only prerequisite being the knowledge of basic functional analysis.
International Nuclear Information System (INIS)
1989-06-01
This report discusses concepts in nuclear theory such as: neutrino nucleosynthesis; double beta decay; neutrino oscillations; chiral symmetry breaking; T invariance; quark propagator; cold fusion; and other related topics
R. Veenhoven (Ruut)
2014-01-01
markdownabstract__Abstract__ Assumptions Livability theory involves the following six key assumptions: 1. Like all animals, humans have innate needs, such as for food, safety, and companionship. 2. Gratification of needs manifests in hedonic experience. 3. Hedonic experience determines how
Non-equilibrium price theories
Helbing, Dirk; Kern, Daniel
2000-11-01
We propose two theories for the formation of stock prices under the condition that the number of available stocks is fixed. Both theories consider the balance equations for cash and several kinds of stocks. They also take into account interest rates, dividends, and transaction costs. The proposed theories have the advantage that they do not require iterative procedures to determine the price, which would be inefficient for simulations with many agents.
SAIDANI Lassaad
2015-01-01
The nokton theory is an attempt to construct a theory adapted to every physical phenomenon. Space and time have been discretized. Its laws are iterative and precise. Probability plays an important role here. At first I defined the notion of image function and its mathematical framework. The notion of nokton and its state are the basis of several definitions. I later defined the canonical image function and the canonical contribution. Two constants have been necessary to define the dynam...
SAIDANI Lassaad
2017-01-01
The nokton theory is an attempt to construct a theory adapted to every physical phenomenon. Space and time have been discretized. Its laws are iterative and precise. Probability plays an important role here. At first I defined the notion of image function and its mathematical framework. The notion of nokton and its state are the basis of several definitions. I later defined the canonical image function and the canonical contribution. Two constants have been necessary to define the dynam...
Gould, Ronald
2012-01-01
This introduction to graph theory focuses on well-established topics, covering primary techniques and including both algorithmic and theoretical problems. The algorithms are presented with a minimum of advanced data structures and programming details. This thoroughly corrected 1988 edition provides insights to computer scientists as well as advanced undergraduates and graduate students of topology, algebra, and matrix theory. Fundamental concepts and notation and elementary properties and operations are the first subjects, followed by examinations of paths and searching, trees, and networks. S
Kerlinger's Criterial Referents Theory Revisited.
Zak, Itai; Birenbaum, Menucha
1980-01-01
Kerlinger's criterial referents theory of attitudes was tested cross-culturally by administering an education attitude referents summated-rating scale to 713 individuals in Israel. The response pattern to criterial and noncriterial referents was examined. Results indicated empirical cross-cultural validity of theory, but questioned measuring…
International Nuclear Information System (INIS)
Veals, Jeffrey D.; Thompson, Donald L.
2014-01-01
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO 2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO 2 elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO 2 group elimination or by a concerted H-atom and nitroalkyl NO 2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO 2 elimination by N–N bond fission, HONO elimination involving the nitramine NO 2 group, HONO elimination involving a nitroalkyl NO 2 group, and finally NO 2 elimination by C–N bond fission
Energy Technology Data Exchange (ETDEWEB)
Veals, Jeffrey D.; Thompson, Donald L. [Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211 (United States)
2014-04-21
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO{sub 2} or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO{sub 2} elimination by N–N and C–N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO{sub 2} group elimination or by a concerted H-atom and nitroalkyl NO{sub 2} group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO{sub 2} elimination by N–N bond fission, HONO elimination involving the nitramine NO{sub 2} group, HONO elimination involving a nitroalkyl NO{sub 2} group, and finally NO{sub 2} elimination by C–N bond fission.
Veals, Jeffrey D.; Thompson, Donald L.
2014-04-01
Density functional theory and ab initio methods are employed to investigate decomposition pathways of 1,3,3-trinitroazetidine initiated by unimolecular loss of NO2 or HONO. Geometry optimizations are performed using M06/cc-pVTZ and coupled-cluster (CC) theory with single, double, and perturbative triple excitations, CCSD(T), is used to calculate accurate single-point energies for those geometries. The CCSD(T)/cc-pVTZ energies for NO2 elimination by N-N and C-N bond fission are, including zero-point energy (ZPE) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can occur by a concerted H-atom and nitramine NO2 group elimination or by a concerted H-atom and nitroalkyl NO2 group elimination via barriers (at the CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of these four decomposition steps from energetically most favored to least favored is: NO2 elimination by N-N bond fission, HONO elimination involving the nitramine NO2 group, HONO elimination involving a nitroalkyl NO2 group, and finally NO2 elimination by C-N bond fission.
Projected coupled cluster theory.
Qiu, Yiheng; Henderson, Thomas M; Zhao, Jinmo; Scuseria, Gustavo E
2017-08-14
Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system or has to artificially break certain symmetries. On the other hand, projected Hartree-Fock theory captures the essential physics of many kinds of strong correlations via symmetry breaking and restoration. In this work, we combine and try to retain the merits of these two methods by applying symmetry projection to broken symmetry coupled cluster wave functions. The non-orthogonal nature of states resulting from the application of symmetry projection operators furnishes particle-hole excitations to all orders, thus creating an obstacle for the exact evaluation of overlaps. Here we provide a solution via a disentanglement framework theory that can be approximated rigorously and systematically. Results of projected coupled cluster theory are presented for molecules and the Hubbard model, showing that spin projection significantly improves unrestricted coupled cluster theory while restoring good quantum numbers. The energy of projected coupled cluster theory reduces to the unprojected one in the thermodynamic limit, albeit at a much slower rate than projected Hartree-Fock.
Kodaira, Kunihiko
2017-01-01
This book deals with the classical theory of Nevanlinna on the value distribution of meromorphic functions of one complex variable, based on minimum prerequisites for complex manifolds. The theory was extended to several variables by S. Kobayashi, T. Ochiai, J. Carleson, and P. Griffiths in the early 1970s. K. Kodaira took up this subject in his course at The University of Tokyo in 1973 and gave an introductory account of this development in the context of his final paper, contained in this book. The first three chapters are devoted to holomorphic mappings from C to complex manifolds. In the fourth chapter, holomorphic mappings between higher dimensional manifolds are covered. The book is a valuable treatise on the Nevanlinna theory, of special interests to those who want to understand Kodaira's unique approach to basic questions on complex manifolds.
International Nuclear Information System (INIS)
Kenyon, I.R.
1986-01-01
Modern theories of the interactions between fundamental particles are all gauge theories. In the case of gravitation, application of this principle to space-time leads to Einstein's theory of general relativity. All the other interactions involve the application of the gauge principle to internal spaces. Electromagnetism serves to introduce the idea of a gauge field, in this case the electromagnetic field. The next example, the strong force, shows unique features at long and short range which have their origin in the self-coupling of the gauge fields. Finally the unification of the description of the superficially dissimilar electromagnetic and weak nuclear forces completes the picture of successes of the gauge principle. (author)
Kinetic theory of radiation effects
International Nuclear Information System (INIS)
Mansur, L.K.
1987-01-01
To help achieve the quantitative and mechanistic understanding of these processes, the kinetic theory of radiation effects has been developed in the DOE basic energy sciences radiation effects and fusion reactor materials programs, as well as in corresponding efforts in other countries. This discipline grapples with a very wide range of phenomena and draws on numerous sub-fields of theory such as defect physics, diffusion, elasticity, chemical reaction rates, phase transformations and thermodynamics. The theory is cast in a mathematical framework of continuum dynamics. Issues particularly relevant to the present inquiry can be viewed from the standpoints of applications of the theory and areas requiring further progress
Stewart, Ian
2003-01-01
Ian Stewart's Galois Theory has been in print for 30 years. Resoundingly popular, it still serves its purpose exceedingly well. Yet mathematics education has changed considerably since 1973, when theory took precedence over examples, and the time has come to bring this presentation in line with more modern approaches.To this end, the story now begins with polynomials over the complex numbers, and the central quest is to understand when such polynomials have solutions that can be expressed by radicals. Reorganization of the material places the concrete before the abstract, thus motivating the g
International Nuclear Information System (INIS)
Sitenko, A.
1991-01-01
This book emerged out of graduate lectures given by the author at the University of Kiev and is intended as a graduate text. The fundamentals of non-relativistic quantum scattering theory are covered, including some topics, such as the phase-function formalism, separable potentials, and inverse scattering, which are not always coverded in textbooks on scattering theory. Criticisms of the text are minor, but the reviewer feels an inadequate index is provided and the citing of references in the Russian language is a hindrance in a graduate text
Sferra, Bobbie A.; Paddock, Susan C.
This booklet describes various theoretical aspects of leadership, including the proper exercise of authority, effective delegation, goal setting, exercise of control, assignment of responsibility, performance evaluation, and group process facilitation. It begins by describing the evolution of general theories of leadership from historic concepts…
Hall, Marshall
2011-01-01
Includes proof of van der Waerden's 1926 conjecture on permanents, Wilson's theorem on asymptotic existence, and other developments in combinatorics since 1967. Also covers coding theory and its important connection with designs, problems of enumeration, and partition. Presents fundamentals in addition to latest advances, with illustrative problems at the end of each chapter. Enlarged appendixes include a longer list of block designs.
Toso, Robert B.
2000-01-01
Inspired by William Glasser's Reality Therapy ideas, Control Theory (CT) is a disciplinary approach that stresses people's ability to control only their own behavior, based on internal motivations to satisfy five basic needs. At one North Dakota high school, CT-trained teachers are the program's best recruiters. (MLH)
de Vreese, C.H.; Lecheler, S.; Mazzoleni, G.; Barnhurst, K.G.; Ikeda, K.; Maia, R.C.M.; Wessler, H.
2016-01-01
Political issues can be viewed from different perspectives and they can be defined differently in the news media by emphasizing some aspects and leaving others aside. This is at the core of news framing theory. Framing originates within sociology and psychology and has become one of the most used
International Nuclear Information System (INIS)
Gong, Ha Soung
2006-12-01
The text book composed of five parts, which are summary of this book, arrangement of electricity theory including electricity nad magnetism, a direct current, and alternating current. It has two dictionary electricity terms for a synonym. The last is an appendix. It is for preparing for test of officer, electricity engineer and fire fighting engineer.
DEFF Research Database (Denmark)
Monthoux, Pierre Guillet de; Statler, Matt
2014-01-01
The recent Carnegie report (Colby, et al., 2011) characterizes the goal of business education as the development of practical wisdom. In this chapter, the authors reframe Scharmer’s Theory U as an attempt to develop practical wisdom by applying certain European philosophical concepts. Specifically...
DEFF Research Database (Denmark)
Guillet de Monthoux, Pierre; Statler, Matt
2017-01-01
The recent Carnegie report (Colby, et al., 2011) characterizes the goal of business education as the development of practical wisdom. In this chapter, the authors reframe Scharmer's Theory U as an attempt to develop practical wisdom by applying certain European philosophical concepts. Specifically...
International Nuclear Information System (INIS)
Tang, W.M.
2001-01-01
This is a summary of the advances in magnetic fusion energy theory research presented at the 17th International Atomic Energy Agency Fusion Energy Conference from 19 24 October, 1998 in Yokohama, Japan. Theory and simulation results from this conference provided encouraging evidence of significant progress in understanding the physics of thermonuclear plasmas. Indeed, the grand challenge for this field is to acquire the basic understanding that can readily enable the innovations which would make fusion energy practical. In this sense, research in fusion energy is increasingly able to be categorized as fitting well the 'Pasteur's Quadrant' paradigm, where the research strongly couples basic science ('Bohr's Quadrant') to technological impact ('Edison's Quadrant'). As supported by some of the work presented at this conference, this trend will be further enhanced by advanced simulations. Eventually, realistic three-dimensional modeling capabilities, when properly combined with rapid and complete data interpretation of results from both experiments and simulations, can contribute to a greatly enhanced cycle of understanding and innovation. Plasma science theory and simulation have provided reliable foundations for this improved modeling capability, and the exciting advances in high-performance computational resources have further accelerated progress. There were 68 papers presented at this conference in the area of magnetic fusion energy theory
Penland, Patrick R.
Three papers are presented which delineate the foundation of theory and principles which underlie the research and instructional approach to communications at the Graduate School of Library and Information Science, University of Pittsburgh. Cybernetic principles provide the integration, and validation is based in part on a situation-producing…
Lee, William H K.
2016-01-01
A complex system consists of many interacting parts, generates new collective behavior through self organization, and adaptively evolves through time. Many theories have been developed to study complex systems, including chaos, fractals, cellular automata, self organization, stochastic processes, turbulence, and genetic algorithms.
Plummer, MD
1986-01-01
This study of matching theory deals with bipartite matching, network flows, and presents fundamental results for the non-bipartite case. It goes on to study elementary bipartite graphs and elementary graphs in general. Further discussed are 2-matchings, general matching problems as linear programs, the Edmonds Matching Algorithm (and other algorithmic approaches), f-factors and vertex packing.
DEFF Research Database (Denmark)
Bertelsen, Olav Wedege; Bødker, Susanne
2003-01-01
the young HCI research tradition. But HCI was already facing problems: lack of consideration for other aspects of human behavior, for interaction with other people, for culture. Cognitive science-based theories lacked means to address several issues that came out of the empirical projects....
Dynamic statistical information theory
Institute of Scientific and Technical Information of China (English)
无
2006-01-01
In recent years we extended Shannon static statistical information theory to dynamic processes and established a Shannon dynamic statistical information theory, whose core is the evolution law of dynamic entropy and dynamic information. We also proposed a corresponding Boltzmman dynamic statistical information theory. Based on the fact that the state variable evolution equation of respective dynamic systems, i.e. Fokker-Planck equation and Liouville diffusion equation can be regarded as their information symbol evolution equation, we derived the nonlinear evolution equations of Shannon dynamic entropy density and dynamic information density and the nonlinear evolution equations of Boltzmann dynamic entropy density and dynamic information density, that describe respectively the evolution law of dynamic entropy and dynamic information. The evolution equations of these two kinds of dynamic entropies and dynamic informations show in unison that the time rate of change of dynamic entropy densities is caused by their drift, diffusion and production in state variable space inside the systems and coordinate space in the transmission processes; and that the time rate of change of dynamic information densities originates from their drift, diffusion and dissipation in state variable space inside the systems and coordinate space in the transmission processes. Entropy and information have been combined with the state and its law of motion of the systems. Furthermore we presented the formulas of two kinds of entropy production rates and information dissipation rates, the expressions of two kinds of drift information flows and diffusion information flows. We proved that two kinds of information dissipation rates (or the decrease rates of the total information) were equal to their corresponding entropy production rates (or the increase rates of the total entropy) in the same dynamic system. We obtained the formulas of two kinds of dynamic mutual informations and dynamic channel
Energy and Rate Determinations to Activate the C-C σ-BOND of Acetone by Gaseous NI^+
Castleberry, Vanessa A.; Dee, S. Jason; Villarroel, Otsmar J.; Laboren, Ivanna E.; Frey, Sarah E.; Bellert, Darrin J.
2009-06-01
A unique application of a custom fabricated photodissociation spectrometer permits the determination of thermodynamic properties (activation energies), reaction rates, and mechanistic details of bare metal cation mediated C-C σ-bond activation in the gas phase. Specifically, the products and rates resulting from the unimolecular decomposition of the Ni^+Acetone (Ni^+Ac) adduct are monitored after absorption of a known amount of energy. The three dissociative products which are observed in high yield are Ni^+, Ni^+CO, and CH3CO^+. The latter two fragment ions result from the activation of a C-C σ-bond. It was found that minimally 14 000 cm^{-1} of energy must be deposited into the adduct ion to induce C-C bond breakage. Preliminary results for the Ni^+ activation of the C-C σ-bond of acetone indicate that there are (at least) two low energy reaction coordinates leading to C-C bond breakage. The lower energy pathway emerges from the doublet ground state with an upper limit to the activation energy of 14 000 cm^{-1} and reaction rate ≈0.14 molecules/μs. The higher energy path is assumed to be along the quartet reaction coordinate with a minimum activation energy of 18 800 cm^{-1} (relative to the ground state) and a slightly slower reaction rate.
DEFF Research Database (Denmark)
Stein, Irene F.; Stelter, Reinhard
2011-01-01
Communication theory covers a wide variety of theories related to the communication process (Littlejohn, 1999). Communication is not simply an exchange of information, in which we have a sender and a receiver. This very technical concept of communication is clearly outdated; a human being...... is not a data processing device. In this chapter, communication is understood as a process of shared meaning-making (Bruner, 1990). Human beings interpret their environment, other people, and themselves on the basis of their dynamic interaction with the surrounding world. Meaning is essential because people...... ascribe specific meanings to their experiences, their actions in life or work, and their interactions. Meaning is reshaped, adapted, and transformed in every communication encounter. Furthermore, meaning is cocreated in dialogues or in communities of practice, such as in teams at a workplace or in school...
2015-01-01
A one-sentence definition of operator theory could be: The study of (linear) continuous operations between topological vector spaces, these being in general (but not exclusively) Fréchet, Banach, or Hilbert spaces (or their duals). Operator theory is thus a very wide field, with numerous facets, both applied and theoretical. There are deep connections with complex analysis, functional analysis, mathematical physics, and electrical engineering, to name a few. Fascinating new applications and directions regularly appear, such as operator spaces, free probability, and applications to Clifford analysis. In our choice of the sections, we tried to reflect this diversity. This is a dynamic ongoing project, and more sections are planned, to complete the picture. We hope you enjoy the reading, and profit from this endeavor.
Helms, Lester L
2014-01-01
Potential Theory presents a clear path from calculus to classical potential theory and beyond, with the aim of moving the reader into the area of mathematical research as quickly as possible. The subject matter is developed from first principles using only calculus. Commencing with the inverse square law for gravitational and electromagnetic forces and the divergence theorem, the author develops methods for constructing solutions of Laplace's equation on a region with prescribed values on the boundary of the region. The latter half of the book addresses more advanced material aimed at those with the background of a senior undergraduate or beginning graduate course in real analysis. Starting with solutions of the Dirichlet problem subject to mixed boundary conditions on the simplest of regions, methods of morphing such solutions onto solutions of Poisson's equation on more general regions are developed using diffeomorphisms and the Perron-Wiener-Brelot method, culminating in application to Brownian motion. In ...
DEFF Research Database (Denmark)
Jensen, Klaus Bruhn
2016-01-01
This article revisits the place of normative and other practical issues in the wider conceptual architecture of communication theory, building on the tradition of philosophical pragmatism. The article first characterizes everyday concepts of communication as the accumulated outcome of natural...... evolution and history: practical resources for human existence and social coexistence. Such practical concepts have served as the point of departure for diverse theoretical conceptions of what communication is. The second part of the article highlights the past neglect and current potential of normative...... communication theories that ask, in addition, what communication ought to be, and what it could be, taking the relationship between communication and justice as a case in point. The final section returns to empirical conceptualizations of different institutions, practices and discourses of communication...
International Nuclear Information System (INIS)
Jarlskog, C.
An introduction to the unified gauge theories of weak and electromagnetic interactions is given. The ingredients of gauge theories and symmetries and conservation laws lead to discussion of local gauge invariance and QED, followed by weak interactions and quantum flavor dynamics. The construction of the standard SU(2)xU(1) model precedes discussion of the unification of weak and electromagnetic interactions and weak neutral current couplings in this model. Presentation of spontaneous symmetry breaking and spontaneous breaking of a local symmetry leads to a spontaneous breaking scheme for the standard SU(2)xU(1) model. Consideration of quarks, leptons, masses and the Cabibbo angles, of the four quark and six quark models and CP violation lead finally to grand unification, followed by discussion of mixing angles in the Georgi-Glashow model, the Higgses of the SU(5) model and proton/ neutron decay in SU(5). (JIW)
International Nuclear Information System (INIS)
Perjes, Z.
1982-01-01
Particle models in twistor theory are reviewed, starting with an introduction into the kinematical-twistor formalism which describes massive particles in Minkowski space-time. The internal transformations of constituent twistors are then discussed. The quantization rules available from a study of twistor scattering situations are used to construct quantum models of fundamental particles. The theory allows the introduction of an internal space with a Kaehlerian metric where hadron structure is described by spherical states of bound constituents. It is conjectured that the spectrum of successive families of hadrons might approach an accumulation point in energy. Above this threshold energy, the Kaehlerian analog of ionization could occur wherein the zero-mass constituents (twistors) of the particle break free. (Auth.)
DEFF Research Database (Denmark)
Carroll, Joseph; Clasen, Mathias; Jonsson, Emelie
2017-01-01
Biocultural theory is an integrative research program designed to investigate the causal interactions between biological adaptations and cultural constructions. From the biocultural perspective, cultural processes are rooted in the biological necessities of the human life cycle: specifically human...... of research as contributions to a coherent, collective research program. This article argues that a mature biocultural paradigm needs to be informed by at least 7 major research clusters: (a) gene-culture coevolution; (b) human life history theory; (c) evolutionary social psychology; (d) anthropological...... forms of birth, growth, survival, mating, parenting, and sociality. Conversely, from the biocultural perspective, human biological processes are constrained, organized, and developed by culture, which includes technology, culturally specific socioeconomic and political structures, religious...
Weber, Rebecca
2012-01-01
What can we compute--even with unlimited resources? Is everything within reach? Or are computations necessarily drastically limited, not just in practice, but theoretically? These questions are at the heart of computability theory. The goal of this book is to give the reader a firm grounding in the fundamentals of computability theory and an overview of currently active areas of research, such as reverse mathematics and algorithmic randomness. Turing machines and partial recursive functions are explored in detail, and vital tools and concepts including coding, uniformity, and diagonalization are described explicitly. From there the material continues with universal machines, the halting problem, parametrization and the recursion theorem, and thence to computability for sets, enumerability, and Turing reduction and degrees. A few more advanced topics round out the book before the chapter on areas of research. The text is designed to be self-contained, with an entire chapter of preliminary material including re...
Veenhoven, Ruut
2014-01-01
markdownabstract__Abstract__ Assumptions Livability theory involves the following six key assumptions: 1. Like all animals, humans have innate needs, such as for food, safety, and companionship. 2. Gratification of needs manifests in hedonic experience. 3. Hedonic experience determines how much we like the life we live (happiness). Hence, happiness depends on need gratification. 4.Need gratification depends on both external living conditions and inner abilities to use these. Hence, bad living...
International Nuclear Information System (INIS)
Casten, R F
2015-01-01
This paper discusses some simple issues that arise in testing models, with a focus on models for low energy nuclear structure. By way of simplified examples, we illustrate some dangers in blind statistical assessments, pointing out especially the need to include theoretical uncertainties, the danger of over-weighting precise or physically redundant experimental results, the need to assess competing theories with independent and physically sensitive observables, and the value of statistical tests properly evaluated. (paper)
Diestel, Reinhard
2017-01-01
This standard textbook of modern graph theory, now in its fifth edition, combines the authority of a classic with the engaging freshness of style that is the hallmark of active mathematics. It covers the core material of the subject with concise yet reliably complete proofs, while offering glimpses of more advanced methods in each field by one or two deeper results, again with proofs given in full detail. The book can be used as a reliable text for an introductory course, as a graduate text, and for self-study. From the reviews: “This outstanding book cannot be substituted with any other book on the present textbook market. It has every chance of becoming the standard textbook for graph theory.”Acta Scientiarum Mathematiciarum “Deep, clear, wonderful. This is a serious book about the heart of graph theory. It has depth and integrity. ”Persi Diaconis & Ron Graham, SIAM Review “The book has received a very enthusiastic reception, which it amply deserves. A masterly elucidation of modern graph theo...
Friedrich, Harald
2016-01-01
This corrected and updated second edition of "Scattering Theory" presents a concise and modern coverage of the subject. In the present treatment, special attention is given to the role played by the long-range behaviour of the projectile-target interaction, and a theory is developed, which is well suited to describe near-threshold bound and continuum states in realistic binary systems such as diatomic molecules or molecular ions. It is motivated by the fact that experimental advances have shifted and broadened the scope of applications where concepts from scattering theory are used, e.g. to the field of ultracold atoms and molecules, which has been experiencing enormous growth in recent years, largely triggered by the successful realization of Bose-Einstein condensates of dilute atomic gases in 1995. The book contains sections on special topics such as near-threshold quantization, quantum reflection, Feshbach resonances and the quantum description of scattering in two dimensions. The level of abstraction is k...
Rating Movies and Rating the Raters Who Rate Them.
Zhou, Hua; Lange, Kenneth
2009-11-01
The movie distribution company Netflix has generated considerable buzz in the statistics community by offering a million dollar prize for improvements to its movie rating system. Among the statisticians and computer scientists who have disclosed their techniques, the emphasis has been on machine learning approaches. This article has the modest goal of discussing a simple model for movie rating and other forms of democratic rating. Because the model involves a large number of parameters, it is nontrivial to carry out maximum likelihood estimation. Here we derive a straightforward EM algorithm from the perspective of the more general MM algorithm. The algorithm is capable of finding the global maximum on a likelihood landscape littered with inferior modes. We apply two variants of the model to a dataset from the MovieLens archive and compare their results. Our model identifies quirky raters, redefines the raw rankings, and permits imputation of missing ratings. The model is intended to stimulate discussion and development of better theory rather than to win the prize. It has the added benefit of introducing readers to some of the issues connected with analyzing high-dimensional data.
Chambers, Christopher P.; Echenique, Federico
2016-01-01
We propose a theory of intertemporal choice that is robust to specific assumptions on the discount rate. One class of models requires that one utility stream be chosen over another if and only if its discounted value is higher for all discount factors in a set. Another model focuses on an average discount factor. Yet another model is pessimistic, and evaluates a flow by the lowest available discounted value.
Quantum mechanics of molecular rate processes
Levine, Raphael D
1999-01-01
This survey of applications of the theory of collisions and rate processes to molecular problems explores collisions of molecules with internal structure, generalized Ehrenfest theorem, theory of reactive collisions, and role of symmetry. It also reviews partitioning technique, equivalent potentials and quasibound states, theory of direct reactions, more. 1969 edition.
Goldie, Charles M
1991-01-01
This book is an introduction, for mathematics students, to the theories of information and codes. They are usually treated separately but, as both address the problem of communication through noisy channels (albeit from different directions), the authors have been able to exploit the connection to give a reasonably self-contained treatment, relating the probabilistic and algebraic viewpoints. The style is discursive and, as befits the subject, plenty of examples and exercises are provided. Some examples and exercises are provided. Some examples of computer codes are given to provide concrete illustrations of abstract ideas.
2009-01-01
This book deals with the basic subjects of design theory. It begins with balanced incomplete block designs, various constructions of which are described in ample detail. In particular, finite projective and affine planes, difference sets and Hadamard matrices, as tools to construct balanced incomplete block designs, are included. Orthogonal latin squares are also treated in detail. Zhu's simpler proof of the falsity of Euler's conjecture is included. The construction of some classes of balanced incomplete block designs, such as Steiner triple systems and Kirkman triple systems, are also given.
International business theory and marketing theory
Soldner, Helmut
1984-01-01
International business theory and marketing theory : elements for internat. marketing theory building. - In: Marketing aspects of international business / Gerald M. Hampton ... (eds.). - Boston u.a. : Kluwer, 1984. - S. 25-57
DEFF Research Database (Denmark)
Lai, Signe Sophus
2015-01-01
tværs af medier og platforme, forskudt i tid og on-demand. This article focuses on audience ratings, which have functioned as the central ‘currency’ informing the media trade. It discusses changes to the production and accuracy of audience ratings at a time when established standards are being...
Dielectronic recombination theory
International Nuclear Information System (INIS)
LaGattuta, K.J.
1991-01-01
A theory now in wide use for the calculation of dielectronic recombination cross sections (σ DR ) and rate coefficients (α DR ) was one introduced originally by Feshbach for nuclear physics applications, and then later adapted for atomic scattering problems by Hahn. In the following, we briefly review this theory in a very general form, which allows one to account for the effects of overlapping and interacting resonances, as well as continuum-continuum coupling. An extension of our notation will then also allow for the inclusion of the effects of direct radiative recombination, along with a treatment of the interference between radiative and dielectronic recombination. Other approaches to the calculation of σ DR have been described by Fano and by Seaton. We will not consider those theories here. Calculations of α DR have progressed considerably over the last 25 years, since the early work of Burgess. Advances in the reliability of theoretical predictions have also been promoted recently b a variety of direct laboratory measurements of σ DR . While the measurements of σ DR for δn ≠ 0 excitations have tended to agree very well with calculations, the case of δn = 0 has been much problematic. However, by invoking a mechanism originally proposed by Jacobs, which takes into account the effect of stray electric fields on high Rydberg states (HRS) participating in the DR process, new calculations have improved the agreement between theory and experiment for these cases. Nevertheless, certain discrepancies still remain
Introduction to quantum field theory
Alvarez-Gaumé, Luís
1994-01-01
The purpose of this lecture is to review some elementary aspects of Quantum Field Theory. From the necessity to introduce quantum fields once quantum mechanics and special relativity are put together, to some of the basic practical computational tools in the subject, including the canonical quantization of simple field theories, the derivation of Feynman rules, computation of cross sections and decay rates, some introductory remarks on the treatment of unstable states and the possible realization of symmetries in a general field theory. The audience is required to have a working knowledge of quantum mechanics and special relativity and it would also be desirable to know the rudiments of relativistic quantum mechanics.
Superradiance in the source theory
International Nuclear Information System (INIS)
Kim, Y.D.
1979-01-01
The radiative transition rate is formulated in a new approach within the framework of the source theory which makes use of a vacuum persistence amplitude. It is also shown that the source theory can be applied effectively to detemine the likelihood of superradiance of coherence in spontaneous emission. Since the source theory is applicable not only to electromagnetic interactions but also to many other interaction, it would be most interesting to inquire if superradiance can occur in processes other than the elctromagnetic radiative process, such as nuclear or gravitational process. (Author)
International Nuclear Information System (INIS)
Gong, Ha Seong
2006-02-01
This book explains electric theory which is divided into four chapters. The first chapter includes electricity and material, electric field, capacitance, magnetic field and electromagnetic force, inductance. The second chapter mentions electronic circuit analysis, electric resistance,heating and power, chemical activity on current and battery with electrolysis. The third chapter deals with an alternating current circuit about the basics of an AC circuit, operating of resistance, inductance and capacitance, series circuit and parallel circuit of PLC, an alternating current circuit, Three-phase Alternating current, two terminal pair network and voltage and current of non-linearity circuit. The last explains transient phenomena of RC series circuit, RL series circuit, transient phenomena of an alternating current circuit and transient phenomena of RLC series circuit.
International Nuclear Information System (INIS)
Nobile, G.
1993-07-01
With reference to highly debated sustainable growth strategies to counter pressing interrelated global environmental and socio-economic problems, this paper reviews economic and resource development theories proposed by classical and neoclassical economists. The review evidences the growing debate among public administration decision makers regarding appropriate methods to assess the worth of natural resources and ecosystems. Proposed methods tend to be biased either towards environmental protection or economic development. Two major difficulties in the effective implementation of sustainable growth strategies are also evidenced - the management of such strategies would require appropriate revisions to national accounting systems, and the dynamic flow of energy and materials between an economic system and the environment would generate a sequence of unstable structures evolving in a chaotic and unpredictable way
Franceschetti, Massimo
2017-01-01
Understand the relationship between information theory and the physics of wave propagation with this expert guide. Balancing fundamental theory with engineering applications, it describes the mechanism and limits for the representation and communication of information using electromagnetic waves. Information-theoretic laws relating functional approximation and quantum uncertainty principles to entropy, capacity, mutual information, rate distortion, and degrees of freedom of band-limited radiation are derived and explained. Both stochastic and deterministic approaches are explored, and applications for sensing and signal reconstruction, wireless communication, and networks of multiple transmitters and receivers are reviewed. With end-of-chapter exercises and suggestions for further reading enabling in-depth understanding of key concepts, it is the ideal resource for researchers and graduate students in electrical engineering, physics and applied mathematics looking for a fresh perspective on classical informat...
A Future of Communication Theory: Systems Theory.
Lindsey, Georg N.
Concepts of general systems theory, cybernetics and the like may provide the methodology for communication theory to move from a level of technology to a level of pure science. It was the purpose of this paper to (1) demonstrate the necessity of applying systems theory to the construction of communication theory, (2) review relevant systems…
International Nuclear Information System (INIS)
Masuda, Takahiro
1994-01-01
Experimental results of inverse dose-rate effect, so-called Kada Effects, which was published by Takakura and her coworkers on radiation-induced strand breaks of plasmid DNA in aerated aqueous solution, have been kinetically analyzed and discussed on the basis of radiation chemistry. the kinetic analysis indicates that there are two possible mechanisms; 1) equilibrium mixture of O 2 - and HO 2 is responsible for strand breaks of DNA, and 2) peroxyl radical produced from citrate is effective for the strand breaks. However, the detailed kinetic analysis revealed that the latter is improbable because unimolecular decay of the peroxyl radical must be assumed to be negligible for its participation despite fast decay of analogous organic peroxyl radicals. The analysis has also given 9.93±0.10 dm 3 mol -1 s -1 per nucleotide unit, which corresponds to 7.62 x 10 4 dm 3 mol -1 s -1 per DNA molecule, as the rate constant for the reaction of the equilibrium mixture with plasmid pBR 322 DNA. Furthermore the probability that the reaction of the mixture with a nucleotide unit of DNA leads to strand breaks was obtained to be 3.36 x 10 -3 for gamma-irradiated system and 1.98 x 10 -3 for beta-irradiated system, respectively. (author)
A Theory of Immersion Freezing
Barahona, Donifan
2017-01-01
Immersion freezing is likely involved in the initiation of precipitation and determines to large extent the phase partitioning in convective clouds. Theoretical models commonly used to describe immersion freezing in atmospheric models are based on the classical nucleation theory which however neglects important interactions near the immersed particle that may affect nucleation rates. This work introduces a new theory of immersion freezing based on two premises. First, immersion ice nucleation is mediated by the modification of the properties of water near the particle-liquid interface, rather than by the geometry of the ice germ. Second, the same mechanism that leads to the decrease in the work of germ formation also decreases the mobility of water molecules near the immersed particle. These two premises allow establishing general thermodynamic constraints to the ice nucleation rate. Analysis of the new theory shows that active sites likely trigger ice nucleation, but they do not control the overall nucleation rate nor the probability of freezing. It also suggests that materials with different ice nucleation efficiency may exhibit similar freezing temperatures under similar conditions but differ in their sensitivity to particle surface area and cooling rate. Predicted nucleation rates show good agreement with observations for a diverse set of materials including dust, black carbon and bacterial ice nucleating particles. The application of the new theory within the NASA Global Earth System Model (GEOS-5) is also discussed.
Energy Technology Data Exchange (ETDEWEB)
Medvedev, V N
1978-01-01
In the most general form, the existing methane-metering equipment which issues command signals when the maximum permissible value of methane concentration has been reached can be viewed as a recognition system. The algorithm for operation on the principle of evaluating the degree of blow-out danger of the ore atmosphere stipulates the recognition of two situations: 1) ''not dangerous ''(methane concentration below maximum permissible value); 2) ''dangerous'' (disorders in technological process; methane concentration above maximum permissible value). This approach for constructing means for gas protection is optimal only for mines working beds which are not dangerous for sudden blow-outs. However, if we ''train'' the apparatus to recognize what was the reason for increase in methane concentration, ways are afforded for solving the problem of creating an effective methane-metering equipment for mines with sudden blow-outs. Gas-dynamic processes with sudden blow-outs can be distinguished from standard technological, in particular, according to the rate in increase in methane concentration. On this basis, functional plan is proposed for constructing the automatic gas protection for explosiondangerous mines which includes a primary measurement of methane concentration, block of concentration control, block of process recognition, block of command signals, block of information delay, block of measuring the rate of methane concentration, threshold device for the rate of increase in concentration.
International Nuclear Information System (INIS)
Queen, N.M.
1978-01-01
This series of lectures on basic scattering theory were given as part of a course for postgraduate high energy physicists and were designed to acquaint the student with some of the basic language and formalism used for the phenomenological description of nuclear reactions and decay processes used for the study of elementary particle interactions. Well established and model independent aspects of scattering theory, which are the basis of S-matrix theory, are considered. The subject is considered under the following headings; the S-matrix, cross sections and decay rates, phase space, relativistic kinematics, the Mandelstam variables, the flux factor, two-body phase space, Dalitz plots, other kinematic plots, two-particle reactions, unitarity, the partial-wave expansion, resonances (single-channel case), multi-channel resonances, analyticity and crossing, dispersion relations, the one-particle exchange model, the density matrix, mathematical properties of the density matrix, the density matrix in scattering processes, the density matrix in decay processes, and the helicity formalism. Some exercises for the students are included. (U.K.)
Holmes, Robert R.; Singh, Vijay P.
2016-01-01
Autonomous direct determination of a continuous time series of streamflow is not economically feasible at present (2014). As such, surrogates are used to derive a continuous time series of streamflow. The derivation process entails developing a streamflow rating, which can range from a simple, single-valued relation between stage and streamflow to a fully dynamic one-dimensional model based on hydraulics of the flow.
Chinese implicit leadership theory.
Ling, W; Chia, R C; Fang, L
2000-12-01
In a 1st attempt to identify an implicit theory of leadership among Chinese people, the authors developed the Chinese Implicit Leadership Scale (CILS) in Study 1. In Study 2, they administered the CILS to 622 Chinese participants from 5 occupation groups, to explore differences in perceptions of leadership. Factor analysis yielded 4 factors of leadership: Personal Morality, Goal Efficiency, Interpersonal Competence, and Versatility. Social groups differing in age, gender, education level, and occupation rated these factors. Results showed no significant gender differences, and the underlying cause for social group differences was education level. All groups gave the highest ratings to Interpersonal Competence, reflecting the enormous importance of this factor, which is consistent with Chinese collectivist values.
MACCIA, ELIZABETH S.; AND OTHERS
AN ANNOTATED BIBLIOGRAPHY OF 20 ITEMS AND A DISCUSSION OF ITS SIGNIFICANCE WAS PRESENTED TO DESCRIBE CURRENT UTILIZATION OF SUBJECT THEORIES IN THE CONSTRUCTION OF AN EDUCATIONAL THEORY. ALSO, A THEORY MODEL WAS USED TO DEMONSTRATE CONSTRUCTION OF A SCIENTIFIC EDUCATIONAL THEORY. THE THEORY MODEL INCORPORATED SET THEORY (S), INFORMATION THEORY…
Evaporation of Lennard-Jones clusters
International Nuclear Information System (INIS)
Roman, C.E.; Garzon, I.L.
1991-01-01
Extensive molecular dynamics simulations have been done to study the evaporation of a 13-atom Lennard-Jones cluster. The survival probability and the evaporative lifetime are calculated as a function of the cluster total energy from a classical trajectory analysis. The results are interpreted in terms of the RRK theory of unimolecular dissociation. The calculation of the binding energy of the evaporated species from the evaporation rate and the average kinetic energy release is discussed. (orig.)
Linking Statistical and Ecological Theory
Harris, Keith; Parsons, Todd L.; Ijaz, Umer Z.; Lahti, Leo; Holmes, Ian; Quince, Christopher
2017-01-01
Neutral models which assume ecological equivalence between species provide null models for community assembly. In Hubbell's unified neutral theory of biodiversity (UNTB), many local communities are connected to a single metacommunity through differing immigration rates. Our ability to fit the
Theory of oxygen isotope exchange
den Otter, M.W.; Boukamp, Bernard A.; Bouwmeester, Henricus J.M.
2001-01-01
Transients for oxygen molecular mass numbers 32, 34 and 36 are derived which can be used for the interpretation of oxygen isotope exchange data based on measurement of concentrations of 16O2, 16O18O and 18O2 in the gas phase. Key parameters in the theory are the rate at which oxygen molecules are
Müller, Gert; Sacks, Gerald
1990-01-01
These proceedings contain research and survey papers from many subfields of recursion theory, with emphasis on degree theory, in particular the development of frameworks for current techniques in this field. Other topics covered include computational complexity theory, generalized recursion theory, proof theoretic questions in recursion theory, and recursive mathematics.
K-theory and representation theory
International Nuclear Information System (INIS)
Kuku, A.O.
2003-01-01
This contribution includes K-theory of orders, group-rings and modules over EI categories, equivariant higher algebraic K-theory for finite, profinite and compact Lie group actions together with their relative generalisations and applications
Gravity, general relativity theory and alternative theories
International Nuclear Information System (INIS)
Zel'dovich, Ya.B.; Grishchuk, L.P.; Moskovskij Gosudarstvennyj Univ.
1986-01-01
The main steps in plotting the current gravitation theory and some prospects of its subsequent development are reviewed. The attention is concentrated on a comparison of the relativistic gravitational field with other physical fields. Two equivalent formulations of the general relativity (GR) - geometrical and field-theoretical - are considered in detail. It is shown that some theories of gravity constructed as the field theories at a flat background space-time are in fact just different formulations of GR and not alternative theories
Becker, Katrin; Becker, Melanie; Schwarz, John H.
String theory is one of the most exciting and challenging areas of modern theoretical physics. This book guides the reader from the basics of string theory to recent developments. It introduces the basics of perturbative string theory, world-sheet supersymmetry, space-time supersymmetry, conformal field theory and the heterotic string, before describing modern developments, including D-branes, string dualities and M-theory. It then covers string geometry and flux compactifications, applications to cosmology and particle physics, black holes in string theory and M-theory, and the microscopic origin of black-hole entropy. It concludes with Matrix theory, the AdS/CFT duality and its generalizations. This book is ideal for graduate students and researchers in modern string theory, and will make an excellent textbook for a one-year course on string theory. It contains over 120 exercises with solutions, and over 200 homework problems with solutions available on a password protected website for lecturers at www.cambridge.org/9780521860697. Comprehensive coverage of topics from basics of string theory to recent developments Ideal textbook for a one-year course in string theory Includes over 100 exercises with solutions Contains over 200 homework problems with solutions available to lecturers on-line
Theoretical and expert system approach to photoionization theories
Directory of Open Access Journals (Sweden)
Petrović Ivan D.
2016-01-01
Full Text Available The influence of the ponderomotive and the Stark shifts on the tunneling transition rate was observed, for non-relativistic linearly polarized laser field for alkali atoms, with three different theoretical models, the Keldysh theory, the Perelomov, Popov, Terent'ev (PPT theory, and the Ammosov, Delone, Krainov (ADK theory. We showed that aforementioned shifts affect the transition rate differently for different approaches. Finally, we presented a simple expert system for analysis of photoionization theories.
Two problems in thermal field theory
Indian Academy of Sciences (India)
In this talk, I review recent progress made in two areas of thermal field theory. In par- ticular, I discuss various approaches for the calculation of the quark gluon plasma thermodynamical properties, and the problem of its photon production rate. Keywords. Thermal field theory; quark-gluon plasma. PACS Nos 11.10.Wx; 12.38.
Social Comparison of Pay and Inequity Theory.
Judd, Ben
Inequity theory differs from social exchange theory in its analysis of a worker's reaction to pay by asserting that effects on work performance caused by high or low pay are due to social comparison of fairness rather than principles of direct exchange, such as reciprocity and power. The present experiment held piece-rate pay constant at two…
A physical theory on placement of fertilizers
Wit, de C.T.
1953-01-01
A theory was developed enabling calculation of the effect of any placement method of fertilizer on yield if the effect of one method is known.
This theory was based on the following established facts. The reactions between soil and fertilizer rate are the same for broadcasting and placement
International Nuclear Information System (INIS)
Bergmann, P.G.
1980-01-01
A problem of construction of the unitary field theory is discussed. The preconditions of the theory are briefly described. The main attention is paid to the geometrical interpretation of physical fields. The meaning of the conceptions of diversity and exfoliation is elucidated. Two unitary field theories are described: the Weyl conformic geometry and Calitzy five-dimensioned theory. It is proposed to consider supersymmetrical theories as a new approach to the problem of a unitary field theory. It is noted that the supergravitational theories are really unitary theories, since the fields figuring there do not assume invariant expansion
Boley, Bruno A
1997-01-01
Highly regarded text presents detailed discussion of fundamental aspects of theory, background, problems with detailed solutions. Basics of thermoelasticity, heat transfer theory, thermal stress analysis, more. 1985 edition.
International Nuclear Information System (INIS)
Marciano, W.J.
1984-12-01
The present state of the art in elementary particle theory is reviewed. Topics include quantum electrodynamics, weak interactions, electroweak unification, quantum chromodynamics, and grand unified theories. 113 references
The theory of heavy flavour production
Energy Technology Data Exchange (ETDEWEB)
Ellis, R.K.
1989-08-09
The theory of heavy quark production in hadronic reactions is reviewed. Rates for the production of charm, bottom and top quarks at energies of current interest are presented. 34 refs., 19 figs., 2 tabs.
The theory of heavy flavour production
International Nuclear Information System (INIS)
Ellis, R.K.
1989-01-01
The theory of heavy quark production in hadronic reactions is reviewed. Rates for the production of charm, bottom and top quarks at energies of current interest are presented. 34 refs., 19 figs., 2 tabs
Boltzmann, Darwin and Directionality theory
Energy Technology Data Exchange (ETDEWEB)
Demetrius, Lloyd A., E-mail: ldemetr@oeb.harvard.edu
2013-09-01
Boltzmann’s statistical thermodynamics is a mathematical theory which relates the macroscopic properties of aggregates of interacting molecules with the laws of their interaction. The theory is based on the concept thermodynamic entropy, a statistical measure of the extent to which energy is spread throughout macroscopic matter. Macroscopic evolution of material aggregates is quantitatively explained in terms of the principle: Thermodynamic entropy increases as the composition of the aggregate changes under molecular collision. Darwin’s theory of evolution is a qualitative theory of the origin of species and the adaptation of populations to their environment. A central concept in the theory is fitness, a qualitative measure of the capacity of an organism to contribute to the ancestry of future generations. Macroscopic evolution of populations of living organisms can be qualitatively explained in terms of a neo-Darwinian principle: Fitness increases as the composition of the population changes under variation and natural selection. Directionality theory is a quantitative model of the Darwinian argument of evolution by variation and selection. This mathematical theory is based on the concept evolutionary entropy, a statistical measure which describes the rate at which an organism appropriates energy from the environment and reinvests this energy into survivorship and reproduction. According to directionality theory, microevolutionary dynamics, that is evolution by mutation and natural selection, can be quantitatively explained in terms of a directionality principle: Evolutionary entropy increases when the resources are diverse and of constant abundance; but decreases when the resource is singular and of variable abundance. This report reviews the analytical and empirical support for directionality theory, and invokes the microevolutionary dynamics of variation and selection to delineate the principles which govern macroevolutionary dynamics of speciation and
Boltzmann, Darwin and Directionality theory
International Nuclear Information System (INIS)
Demetrius, Lloyd A.
2013-01-01
Boltzmann’s statistical thermodynamics is a mathematical theory which relates the macroscopic properties of aggregates of interacting molecules with the laws of their interaction. The theory is based on the concept thermodynamic entropy, a statistical measure of the extent to which energy is spread throughout macroscopic matter. Macroscopic evolution of material aggregates is quantitatively explained in terms of the principle: Thermodynamic entropy increases as the composition of the aggregate changes under molecular collision. Darwin’s theory of evolution is a qualitative theory of the origin of species and the adaptation of populations to their environment. A central concept in the theory is fitness, a qualitative measure of the capacity of an organism to contribute to the ancestry of future generations. Macroscopic evolution of populations of living organisms can be qualitatively explained in terms of a neo-Darwinian principle: Fitness increases as the composition of the population changes under variation and natural selection. Directionality theory is a quantitative model of the Darwinian argument of evolution by variation and selection. This mathematical theory is based on the concept evolutionary entropy, a statistical measure which describes the rate at which an organism appropriates energy from the environment and reinvests this energy into survivorship and reproduction. According to directionality theory, microevolutionary dynamics, that is evolution by mutation and natural selection, can be quantitatively explained in terms of a directionality principle: Evolutionary entropy increases when the resources are diverse and of constant abundance; but decreases when the resource is singular and of variable abundance. This report reviews the analytical and empirical support for directionality theory, and invokes the microevolutionary dynamics of variation and selection to delineate the principles which govern macroevolutionary dynamics of speciation and
Jardine, John F
2015-01-01
This monograph on the homotopy theory of topologized diagrams of spaces and spectra gives an expert account of a subject at the foundation of motivic homotopy theory and the theory of topological modular forms in stable homotopy theory. Beginning with an introduction to the homotopy theory of simplicial sets and topos theory, the book covers core topics such as the unstable homotopy theory of simplicial presheaves and sheaves, localized theories, cocycles, descent theory, non-abelian cohomology, stacks, and local stable homotopy theory. A detailed treatment of the formalism of the subject is interwoven with explanations of the motivation, development, and nuances of ideas and results. The coherence of the abstract theory is elucidated through the use of widely applicable tools, such as Barr's theorem on Boolean localization, model structures on the category of simplicial presheaves on a site, and cocycle categories. A wealth of concrete examples convey the vitality and importance of the subject in topology, n...
Production of sensitivity and false alarm rate
International Nuclear Information System (INIS)
Han Zijie; Kang Wu; Chu Chengsheng; Hao Fanhua; Liu Xiaoya; Cao Lin; Hu Yongbo; Gong Jian; Xiang Yongchun; Zhang Jianhua; Yang Xiangdong
2007-01-01
The false alarm rate and sensitivity in nuclear material monitoring system are affected by alarm principle. Two different alarm principles are studied with theory and experiment analysis in this paper. Our research shows that theory analysis and experiment result are accordant very much. This study provides technology support for designing better alarm principle in nuclear material monitoring system. (authors)
Theory of tapered laser cooling
International Nuclear Information System (INIS)
Okamoto, Hiromi; Wei, J.
1998-01-01
A theory of tapered laser cooling for fast circulating ion beams in a storage ring is constructed. The authors describe the fundamentals of this new cooling scheme, emphasizing that it might be the most promising way to beam crystallization. The cooling rates are analytically evaluated to study the ideal operating condition. They discuss the physical implication of the tapering factor of cooling laser, and show how to determine its optimum value. Molecular dynamics method is employed to demonstrate the validity of the present theory
The Simplest Unified Growth Theory
DEFF Research Database (Denmark)
Strulik, Holger; Weisdorf, Jacob Louis
This paper provides a unified growth theory, i.e. a model that explains the very long-run economic and demographic development path of industrialized economies, stretching from the pre-industrial era to present-day and beyond. Making strict use of Malthus' (1798) so-called preventive check...... hypothesis - that fertility rates vary inversely with the price of food - the current study offers a new and straightforward explanation for the demographic transition and the break with the Malthusian era. The current framework lends support to existing unified growth theories and is well in tune...
Rationality, Theory Acceptance and Decision Theory
Directory of Open Access Journals (Sweden)
J. Nicolas Kaufmann
1998-06-01
Full Text Available Following Kuhn's main thesis according to which theory revision and acceptance is always paradigm relative, I propose to outline some possible consequences of such a view. First, asking the question in what sense Bayesian decision theory could serve as the appropriate (normative theory of rationality examined from the point of view of the epistemology of theory acceptance, I argue that Bayesianism leads to a narrow conception of theory acceptance. Second, regarding the different types of theory revision, i.e. expansion, contraction, replacement and residuals shifts, I extract from Kuhn's view a series of indications showing that theory replacement cannot be rationalized within the framework of Bayesian decision theory, not even within a more sophisticated version of that model. Third, and finally, I will point to the need for a more comprehensive model of rationality than the Bayesian expected utility maximization model, the need for a model which could better deal with the different aspects of theory replacement. I will show that Kuhn's distinction between normal and revolutionary science gives us several hints for a more adequate theory of rationality in science. I will also show that Kuhn is not in a position to fully articulate his main ideas and that he well be confronted with a serious problem concerning collective choice of a paradigm.
From chaos to unification: U theory vs. M theory
International Nuclear Information System (INIS)
Ye, Fred Y.
2009-01-01
A unified physical theory called U theory, that is different from M theory, is defined and characterized. U theory, which includes spinor and twistor theory, loop quantum gravity, causal dynamical triangulations, E-infinity unification theory, and Clifford-Finslerian unifications, is based on physical tradition and experimental foundations. In contrast, M theory pays more attention to mathematical forms. While M theory is characterized by supersymmetry string theory, U theory is characterized by non-supersymmetry unified field theory.
Contemporary theories of democracy
Directory of Open Access Journals (Sweden)
Mladenović Ivan
2008-01-01
Full Text Available The aim of this paper is two-fold: first, to analyze several contemporary theories of democracy, and secondly, to propose a theoretical framework for further investigations based on analyzed theories. The following four theories will be analyzed: pluralism, social choice theory, deliberative democracy and participatory democracy.
Moschovakis, YN
1987-01-01
Now available in paperback, this monograph is a self-contained exposition of the main results and methods of descriptive set theory. It develops all the necessary background material from logic and recursion theory, and treats both classical descriptive set theory and the effective theory developed by logicians.
't Hooft, Gerardus; Witten, Edward
2005-01-01
In his later years, Einstein sought a unified theory that would extend general relativity and provide an alternative to quantum theory. There is now talk of a "theory of everything"; fifty years after his death, how close are we to such a theory? (3 pages)
de Bruin, B.P.
2005-01-01
Game theory is the mathematical study of strategy and conflict. It has wide applications in economics, political science, sociology, and, to some extent, in philosophy. Where rational choice theory or decision theory is concerned with individual agents facing games against nature, game theory deals
Chudnovsky, A.
1987-01-01
A damage parameter is introduced in addition to conventional parameters of continuum mechanics and consider a crack surrounded by an array of microdefects within the continuum mechanics framework. A system consisting of the main crack and surrounding damage is called crack layer (CL). Crack layer propagation is an irreversible process. The general framework of the thermodynamics of irreversible processes are employed to identify the driving forces (causes) and to derive the constitutive equation of CL propagation, that is, the relationship between the rates of the crack growth and damage dissemination from one side and the conjugated thermodynamic forces from another. The proposed law of CL propagation is in good agreement with the experimental data on fatigue CL propagation in various materials. The theory also elaborates material toughness characterization.
Microscopic Theory of Transconductivity
Directory of Open Access Journals (Sweden)
A. P. Jauho
1998-01-01
Full Text Available Measurements of momentum transfer between two closely spaced mesoscopic electronic systems, which couple via Coulomb interaction but where tunneling is inhibited, have proven to be a fruitful method of extracting information about interactions in mesoscopic systems. We report a fully microscopic theory for transconductivity σ12, or, equivalently, momentum transfer rate between the system constituents. Our main formal result expresses the transconductivity in terms of two fluctuation diagrams, which are topologically related, but not equivalent to, the Azlamazov-Larkin and Maki-Thompson diagrams known for superconductivity. In the present paper the magnetic field dependence of σ12 is discussed, and we find that σ12(B is strongly enhanced over its zero field value, and it displays strong features, which can be understood in terms of a competition between density-of-states and screening effects.
Institute of Scientific and Technical Information of China (English)
无
2003-01-01
The basic ideas of game theory were originated from the problems of maximum and minimum given by J.Yon Neumann in 1928. Later, wars accelerated the study of game theory, there are many developments that contributed to the advancement of game theory, many problems of optimum appeared in economic development process. Scientists applied mathematic methods to studying game theory to make the theory more profound and perfect. The axiomatic structure of game theory was nearly complete in 1944. The path of the development of game theory started from finite to infinite, from two players to many players, from expressing gains with quantity to showing the ending of game theory with abstract result, and from certainty problems to random problems. Thus development of game theory is closely related to the economic development. In recent years, the research on the non-differentiability of Shapley value posed by Belgian Mertens is one of the advanced studies in game theory.
Nonrelativistic superstring theories
International Nuclear Information System (INIS)
Kim, Bom Soo
2007-01-01
We construct a supersymmetric version of the critical nonrelativistic bosonic string theory [B. S. Kim, Phys. Rev. D 76, 106007 (2007).] with its manifest global symmetry. We introduce the anticommuting bc conformal field theory (CFT) which is the super partner of the βγ CFT. The conformal weights of the b and c fields are both 1/2. The action of the fermionic sector can be transformed into that of the relativistic superstring theory. We explicitly quantize the theory with manifest SO(8) symmetry and find that the spectrum is similar to that of type IIB superstring theory. There is one notable difference: the fermions are nonchiral. We further consider noncritical generalizations of the supersymmetric theory using the superspace formulation. There is an infinite range of possible string theories similar to the supercritical string theories. We comment on the connection between the critical nonrelativistic string theory and the lightlike linear dilaton theory
Nonrelativistic closed string theory
International Nuclear Information System (INIS)
Gomis, Jaume; Ooguri, Hirosi
2001-01-01
We construct a Galilean invariant nongravitational closed string theory whose excitations satisfy a nonrelativistic dispersion relation. This theory can be obtained by taking a consistent low energy limit of any of the conventional string theories, including the heterotic string. We give a finite first order worldsheet Hamiltonian for this theory and show that this string theory has a sensible perturbative expansion, interesting high energy behavior of scattering amplitudes and a Hagedorn transition of the thermal ensemble. The strong coupling duals of the Galilean superstring theories are considered and are shown to be described by an eleven-dimensional Galilean invariant theory of light membrane fluctuations. A new class of Galilean invariant nongravitational theories of light-brane excitations are obtained. We exhibit dual formulations of the strong coupling limits of these Galilean invariant theories and show that they exhibit many of the conventional dualities of M theory in a nonrelativistic setting
Kinetic theory of free electron lasers
Energy Technology Data Exchange (ETDEWEB)
Hafizi, B. [Naval Research Lab., Washington, DC (United States); Roberson, C.W. [Office of Naval Research, Arlington, VA (United States)
1995-12-31
We have developed a relativistic kinetic theory of free electron lasers (FELs). The growth rate, efficiency, filling factor and radius of curvature of the radiation wave fronts are determined. We have used the theory to examine the effects of beam compression on growth rate. The theory has been extended to include self field effects on FEL operation. These effects are particularly important in compact, low voltage FELs. The surprising result is that the self field contribution to the beam quality is opposite to the emittance contribution. Hence self fields can improve beam quality, particularly in compact, low voltage FELs.
Gauge theory loop operators and Liouville theory
International Nuclear Information System (INIS)
Drukker, Nadav; Teschner, Joerg
2009-10-01
We propose a correspondence between loop operators in a family of four dimensional N=2 gauge theories on S 4 - including Wilson, 't Hooft and dyonic operators - and Liouville theory loop operators on a Riemann surface. This extends the beautiful relation between the partition function of these N=2 gauge theories and Liouville correlators found by Alday, Gaiotto and Tachikawa. We show that the computation of these Liouville correlators with the insertion of a Liouville loop operator reproduces Pestun's formula capturing the expectation value of a Wilson loop operator in the corresponding gauge theory. We prove that our definition of Liouville loop operators is invariant under modular transformations, which given our correspondence, implies the conjectured action of S-duality on the gauge theory loop operators. Our computations in Liouville theory make an explicit prediction for the exact expectation value of 't Hooft and dyonic loop operators in these N=2 gauge theories. The Liouville loop operators are also found to admit a simple geometric interpretation within quantum Teichmueller theory as the quantum operators representing the length of geodesics. We study the algebra of Liouville loop operators and show that it gives evidence for our proposal as well as providing definite predictions for the operator product expansion of loop operators in gauge theory. (orig.)
Identity theory and personality theory: mutual relevance.
Stryker, Sheldon
2007-12-01
Some personality psychologists have found a structural symbolic interactionist frame and identity theory relevant to their work. This frame and theory, developed in sociology, are first reviewed. Emphasized in the review are a multiple identity conception of self, identities as internalized expectations derived from roles embedded in organized networks of social interaction, and a view of social structures as facilitators in bringing people into networks or constraints in keeping them out, subsequently, attention turns to a discussion of the mutual relevance of structural symbolic interactionism/identity theory and personality theory, looking to extensions of the current literature on these topics.
Towards a theory of spacetime theories
Schiemann, Gregor; Scholz, Erhard
2017-01-01
This contributed volume is the result of a July 2010 workshop at the University of Wuppertal Interdisciplinary Centre for Science and Technology Studies which brought together world-wide experts from physics, philosophy and history, in order to address a set of questions first posed in the 1950s: How do we compare spacetime theories? How do we judge, objectively, which is the “best” theory? Is there even a unique answer to this question? The goal of the workshop, and of this book, is to contribute to the development of a meta-theory of spacetime theories. Such a meta-theory would reveal insights about specific spacetime theories by distilling their essential similarities and differences, deliver a framework for a class of theories that could be helpful as a blueprint to build other meta-theories, and provide a higher level viewpoint for judging which theory most accurately describes nature. But rather than drawing a map in broad strokes, the focus is on particularly rich regions in the “space of spaceti...
Gauge theory loop operators and Liouville theory
Energy Technology Data Exchange (ETDEWEB)
Drukker, Nadav [Humboldt Univ. Berlin (Germany). Inst. fuer Physik; Gomis, Jaume; Okuda, Takuda [Perimeter Inst. for Theoretical Physics, Waterloo, ON (Canada); Teschner, Joerg [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
2009-10-15
We propose a correspondence between loop operators in a family of four dimensional N=2 gauge theories on S{sup 4} - including Wilson, 't Hooft and dyonic operators - and Liouville theory loop operators on a Riemann surface. This extends the beautiful relation between the partition function of these N=2 gauge theories and Liouville correlators found by Alday, Gaiotto and Tachikawa. We show that the computation of these Liouville correlators with the insertion of a Liouville loop operator reproduces Pestun's formula capturing the expectation value of a Wilson loop operator in the corresponding gauge theory. We prove that our definition of Liouville loop operators is invariant under modular transformations, which given our correspondence, implies the conjectured action of S-duality on the gauge theory loop operators. Our computations in Liouville theory make an explicit prediction for the exact expectation value of 't Hooft and dyonic loop operators in these N=2 gauge theories. The Liouville loop operators are also found to admit a simple geometric interpretation within quantum Teichmueller theory as the quantum operators representing the length of geodesics. We study the algebra of Liouville loop operators and show that it gives evidence for our proposal as well as providing definite predictions for the operator product expansion of loop operators in gauge theory. (orig.)
DEFF Research Database (Denmark)
Andersen, Jack
2015-01-01
Purpose To provide a small overview of genre theory and its associated concepts and to show how genre theory has had its antecedents in certain parts of the social sciences and not in the humanities. Findings The chapter argues that the explanatory force of genre theory may be explained with its...... emphasis on everyday genres, de facto genres. Originality/value By providing an overview of genre theory, the chapter demonstrates the wealth and richness of forms of explanations in genre theory....
Conlon, Joseph
2016-01-01
Is string theory a fraud or one of the great scientific advances? Why do so many physicists work on string theory if it cannot be tested? This book provides insight into why such a theory, with little direct experimental support, plays such a prominent role in theoretical physics. The book gives a modern and accurate account of string theory and science, explaining what string theory is, why it is regarded as so promising, and why it is hard to test.
Teaching Theory X and Theory Y in Organizational Communication
Noland, Carey
2014-01-01
The purpose of the activity described here is to integrate McGregor's Theory X and Theory Y into a group application: design a syllabus that embodies either Theory X or Theory Y tenets. Students should be able to differentiate between Theory X and Theory Y, create a syllabus based on Theory X or Theory Y tenets, evaluate the different syllabi…
Unimolecular Logic Gate with Classical Input by Single Gold Atoms.
Skidin, Dmitry; Faizy, Omid; Krüger, Justus; Eisenhut, Frank; Jancarik, Andrej; Nguyen, Khanh-Hung; Cuniberti, Gianaurelio; Gourdon, Andre; Moresco, Francesca; Joachim, Christian
2018-02-27
By a combination of solution and on-surface chemistry, we synthesized an asymmetric starphene molecule with two long anthracenyl input branches and a short naphthyl output branch on the Au(111) surface. Starting from this molecule, we could demonstrate the working principle of a single molecule NAND logic gate by selectively contacting single gold atoms by atomic manipulation to the longer branches of the molecule. The logical input "1" ("0") is defined by the interaction (noninteraction) of a gold atom with one of the input branches. The output is measured by scanning tunneling spectroscopy following the shift in energy of the electronic tunneling resonances at the end of the short branch of the molecule.
Unimolecular Polypharmacy for Treatment of Diabetes and Obesity
DEFF Research Database (Denmark)
Tschöp, Matthias H; Finan, Brian; Clemmensen, Christoffer
2016-01-01
Many complex diseases have historically proven to be defiant to the best mono-therapeutic approaches. Several examples of combination therapies have largely overcome such challenges, notably for the treatment of severe hypertension and tuberculosis. Obesity and its consequences, such as type 2...... diabetes, have proven to be equally resistant to therapeutic approaches based on single medicines. Proper management of type 2 diabetes often requires adjunctive medications, and the recent registration of a few compound mixtures has set the precedent for combinatorial treatment of obesity. On the other...... to reverse obesity and type 2 diabetes. Here, we summarize the discovery, pre-clinical validation, and first clinical test of such peptide hormone poly-agonist drug candidates....
Crossed molecular beam studies of unimolecular reaction dynamics
International Nuclear Information System (INIS)
Buss, R.J.
1979-04-01
The study of seven radical-molecule reactions using the crossed molecular beam technique with supersonic nozzle beams is reported. Product angular and velocity distributions were obtained and compared with statistical calculations in order to identify dynamical features of the reactions. In the reaction of chlorine and fluorine atoms with vinyl bromide, the product energy distributions are found to deviate from predictions of the statistical model. A similar effect is observed in the reaction of chlorine atoms with 1, 2 and 3-bromopropene. The reaction of oxygen atoms with ICl and CF 3 I has been used to obtain an improved value of the IO bond energy, 55.0 +- 2.0 kcal mol -1 . In all reactions studied, the product energy and angular distributions are found to be coupled, and this is attributed to a kinematic effect of the conservation of angular momentum
Unimolecular Solvolyses in Ionic Liquid: Alcohol Dual Solvent Systems
Directory of Open Access Journals (Sweden)
Elizabeth D. Kochly
2016-01-01
Full Text Available A study was undertaken of the solvolysis of pivaloyl triflate in a variety of ionic liquid:alcohol solvent mixtures. The solvolysis is a kΔ process (i.e., a process in which ionization occurs with rearrangement, and the resulting rearranged carbocation intermediate reacts with the alcohol cosolvent via two competing pathways: nucleophilic attack or elimination of a proton. Five different ionic liquids and three different alcohol cosolvents were investigated to give a total of fifteen dual solvent systems. 1H-NMR analysis was used to determine relative amounts of elimination and substitution products. It was found, not surprisingly, that increasing the bulkiness of alcohol cosolvent led to increased elimination product. The change in the amount of elimination product with increasing ionic liquid concentration, however, varied greatly between ionic liquids. These differences correlate strongly, though not completely, to the Kamlet–Taft solvatochromic parameters of the hydrogen bond donating and accepting ability of the solvent systems. An additional factor playing into these differences is the bulkiness of the ionic liquid anion.
Direction: unified theory of interactions
International Nuclear Information System (INIS)
Valko, P.
1987-01-01
Briefly characterized are the individual theories, namely, the general relativity theory, the Kaluza-Klein theory, the Weyl theory, the unified theory of electromagnetic and weak interactions, the supergravity theory, and the superstring theory. The history is recalled of efforts aimed at creating a unified theory of interactions, and future prospects are outlined. (M.D.). 2 figs
Multipactor theory for multicarrier signals
International Nuclear Information System (INIS)
Anza, S.; Vicente, C.; Gil, J.; Mattes, M.; Raboso, D.; Boria, V. E.; Gimeno, B.
2011-01-01
This work presents a new theory of multipactor under multicarrier signals for parallel-plate geometries, assuming a homogeneous electric field and one-dimensional electron motion. It is the generalization of the nonstationary multipactor theory for single-carrier signals [S. Anza et al.,Phys. Plasmas 17, 062110 (2010)]. It is valid for multicarrier signals with an arbitrary number of carriers with different amplitude, arbitrary frequency, and phase conditions and for any material coating. This new theory is able to model the real dynamics of the electrons during the multipactor discharge for both single and double surface interactions. Among other parameters of the discharge, it calculates the evolution in time of the charge growth, electron absorption, and creation rates as well as the instantaneous secondary emission yield and order. An extensive set of numerical tests with particle-in-cell software has been carried out in order to validate the theory under many different conditions. This theoretical development constitutes the first multipactor theory which completely characterizes the multipactor discharge for arbitrary multicarrier signals, setting the first step for further investigations in the field.
The Neutral Interest Rate: Estimates for Chile
Rodrigo Fuentes S; Fabián Gredig U.
2008-01-01
To estimate the neutral real interest rate for Chile, we use a variety of methods that can be classified into three categories: those derived from economic theory, the neutral rate implicit in financial assets, and statistical procedures using macroeconomic data. We conclude that the neutral rate is not constant over time, but it is closely related with—though not equivalent to—the potential GDP growth rate. The application of the different methods yields fairly similar results. The neutral r...
Building theory through design
DEFF Research Database (Denmark)
Markussen, Thomas
2017-01-01
This chapter deals with a fundamental matter of concern in research through design: how can design work lead to the building of new theory? Controversy exists about the balance between theory and design work in research through design. While some researchers see theory production as the scientific...... hallmark of this type of research, others argue for design work being the primary achievement, with theory serving the auxiliary function of inspiring new designs. This paper demonstrates how design work and theory can be appreciated as two equally important outcomes of research through design. To set...... the scene, it starts out by briefly examining ideas on this issue presented in existing research literature. Hereafter, it introduces three basic forms in which design work can lead to theory that is referred to as extending theories, scaffolding theories and blending theories. Finally, it is discussed how...
Generalizability Theory and Classical Test Theory
Brennan, Robert L.
2011-01-01
Broadly conceived, reliability involves quantifying the consistencies and inconsistencies in observed scores. Generalizability theory, or G theory, is particularly well suited to addressing such matters in that it enables an investigator to quantify and distinguish the sources of inconsistencies in observed scores that arise, or could arise, over…
International Nuclear Information System (INIS)
Kaku, M.
1987-01-01
In this article, the authors summarize the rapid progress in constructing string field theory actions, such as the development of the covariant BRST theory. They also present the newer geometric formulation of string field theory, from which the BRST theory and the older light cone theory can be derived from first principles. This geometric formulation allows us to derive the complete field theory of strings from two geometric principles, in the same way that general relativity and Yang-Mills theory can be derived from two principles based on global and local symmetry. The geometric formalism therefore reduces string field theory to a problem of finding an invariant under a new local gauge group they call the universal string group (USG). Thus, string field theory is the gauge theory of the universal string group in much the same way that Yang-Mills theory is the gauge theory of SU(N). The geometric formulation places superstring theory on the same rigorous group theoretical level as general relativity and gauge theory
Boltzmann, Darwin and Directionality theory
Demetrius, Lloyd A.
2013-09-01
Boltzmann’s statistical thermodynamics is a mathematical theory which relates the macroscopic properties of aggregates of interacting molecules with the laws of their interaction. The theory is based on the concept thermodynamic entropy, a statistical measure of the extent to which energy is spread throughout macroscopic matter. Macroscopic evolution of material aggregates is quantitatively explained in terms of the principle: Thermodynamic entropy increases as the composition of the aggregate changes under molecular collision. Darwin’s theory of evolution is a qualitative theory of the origin of species and the adaptation of populations to their environment. A central concept in the theory is fitness, a qualitative measure of the capacity of an organism to contribute to the ancestry of future generations. Macroscopic evolution of populations of living organisms can be qualitatively explained in terms of a neo-Darwinian principle: Fitness increases as the composition of the population changes under variation and natural selection. Directionality theory is a quantitative model of the Darwinian argument of evolution by variation and selection. This mathematical theory is based on the concept evolutionary entropy, a statistical measure which describes the rate at which an organism appropriates energy from the environment and reinvests this energy into survivorship and reproduction. According to directionality theory, microevolutionary dynamics, that is evolution by mutation and natural selection, can be quantitatively explained in terms of a directionality principle: Evolutionary entropy increases when the resources are diverse and of constant abundance; but decreases when the resource is singular and of variable abundance. This report reviews the analytical and empirical support for directionality theory, and invokes the microevolutionary dynamics of variation and selection to delineate the principles which govern macroevolutionary dynamics of speciation and
Progress on study of nuclear data theory and related fields at the Theory Group of CNDC
Energy Technology Data Exchange (ETDEWEB)
Zhigang, Ge [China Nuclear Data Center, CIAE (China)
1996-06-01
The Theory Group of CNDC (China Nuclear Data Center) has made a lot of progress in nuclear reaction theory and its application as well as many other related fields in 1995. The recent progress in nuclear reaction theory study and its applications, the recent progress in the nuclear data calculation and related code development are introduced. The production rate of radioactive nuclear beam induced by 70 MeV protons on {sup 72}Ge target were calculated. The calculated results are presented.
Keynes's theories of money and banking in the Treatise and The General Theory
John Smithin
2013-01-01
This paper identifies what seem to have been the five main issues in contention in monetary theory, both historically and in the current era, and discusses the view that J.M. Keynes took on each of them in the Treatise on Money and The General Theory. The key issues in monetary theory are the ontology of money, endogenous versus exogenous money, interest-rate determination, the choice of the monetary policy instrument, and the neutrality versus non-neutrality of money.
Interest Rates and Coupon Bonds in Quantum Finance
Baaquie, Belal E.
2009-09-01
1. Synopsis; 2. Interest rates and coupon bonds; 3. Options and option theory; 4. Interest rate and coupon bond options; 5. Quantum field theory of bond forward interest rates; 6. Libor Market Model of interest rates; 7. Empirical analysis of forward interest rates; 8. Libor Market Model of interest rate options; 9. Numeraires for bond forward interest rates; 10. Empirical analysis of interest rate caps; 11. Coupon bond European and Asian options; 12. Empirical analysis of interest rate swaptions; 13. Correlation of coupon bond options; 14. Hedging interest rate options; 15. Interest rate Hamiltonian and option theory; 16. American options for coupon bonds and interest rates; 17. Hamiltonian derivation of coupon bond options; Appendixes; Glossaries; List of symbols; Reference; Index.
Stochastic theory of fatigue corrosion
Hu, Haiyun
1999-10-01
A stochastic theory of corrosion has been constructed. The stochastic equations are described giving the transportation corrosion rate and fluctuation corrosion coefficient. In addition the pit diameter distribution function, the average pit diameter and the most probable pit diameter including other related empirical formula have been derived. In order to clarify the effect of stress range on the initiation and growth behaviour of pitting corrosion, round smooth specimen were tested under cyclic loading in 3.5% NaCl solution.
Social theory and infant feeding
2011-01-01
Clinicians, public health advisors, nutritionists and others have been attempting to increase breastfeeding rates for the last few decades, with varying degrees of success. We need social science researchers to help us understand the role of infant feeding in the family. Some researchers in the area of food and nutrition have found Pierre Bourdieu's theoretical framework helpful. In this editorial, I introduce some of Bourdieu's ideas and suggest researchers interested in infant feeding should consider testing these theories. PMID:21676218
Effective quantum field theories
International Nuclear Information System (INIS)
Georgi, H.M.
1993-01-01
The most appropriate description of particle interactions in the language of quantum field theory depends on the energy at which the interactions are studied; the description is in terms of an ''effective field theory'' that contains explicit reference only to those particles that are actually important at the energy being studied. The various themes of the article are: local quantum field theory, quantum electrodynamics, new physics, dimensional parameters and renormalizability, socio-dynamics of particle theory, spontaneously broken gauge theories, scale dependence, grand unified and effective field theories. 2 figs
Directory of Open Access Journals (Sweden)
Vivian B. Martin, Ph.D.
2005-03-01
Full Text Available Bookshelf will provide critical reviews and perspectives on books on theory and methodology of interest to grounded theory. This issue includes a review of Heaton’s Reworking Qualitative Data, of special interest for some of its references to grounded theory as a secondary analysis tool; and Goulding’s Grounded Theory: A practical guide for management, business, and market researchers, a book that attempts to explicate the method and presents a grounded theory study that falls a little short of the mark of a fully elaborated theory.Reworking Qualitative Data, Janet Heaton (Sage, 2004. Paperback, 176 pages, $29.95. Hardcover also available.
Schürmann, Michael
2008-01-01
This volume contains the revised and completed notes of lectures given at the school "Quantum Potential Theory: Structure and Applications to Physics," held at the Alfried-Krupp-Wissenschaftskolleg in Greifswald from February 26 to March 10, 2007. Quantum potential theory studies noncommutative (or quantum) analogs of classical potential theory. These lectures provide an introduction to this theory, concentrating on probabilistic potential theory and it quantum analogs, i.e. quantum Markov processes and semigroups, quantum random walks, Dirichlet forms on C* and von Neumann algebras, and boundary theory. Applications to quantum physics, in particular the filtering problem in quantum optics, are also presented.
Historicizing affordance theory
DEFF Research Database (Denmark)
Pedersen, Sofie; Bang, Jytte Susanne
2017-01-01
The aim of this article is to discuss how mutually enriching points from both affordance theory and cultural-historical activity theory can promote theoretical ideas which may prove useful as analytical tools for the study of human life and human development. There are two issues that need...... to be overcome in order to explore the potentials of James Gibson’s affordance theory: it does not sufficiently theorize (a) development and (b) society. We claim that Gibson’s affordance theory still needs to be brought beyond “the axiom of immediacy.” Ambivalences in Gibson’s affordance theory...... societal character of affordance theory....
Dynamic Theory: some shock wave and energy implications
International Nuclear Information System (INIS)
Williams, P.E.
1981-02-01
The Dynamic Theory, a unifying five-dimensional theory of space, time, and matter, is examined. The theory predicts an observed discrepancy between shock wave viscosity measurements at low and high pressures in aluminum, a limiting mass-to-energy conversion rate consistent with the available data, and reduced pressures in electromagneticaly contained controlled-fusion plasmas
Developing an Asteroid Rotational Theory
Geis, Gena; Williams, Miguel; Linder, Tyler; Pakey, Donald
2018-01-01
The goal of this project is to develop a theoretical asteroid rotational theory from first principles. Starting at first principles provides a firm foundation for computer simulations which can be used to analyze multiple variables at once such as size, rotation period, tensile strength, and density. The initial theory will be presented along with early models of applying the theory to the asteroid population. Early results confirm previous work by Pravec et al. (2002) that show the majority of the asteroids larger than 200m have negligible tensile strength and have spin rates close to their critical breakup point. Additionally, results show that an object with zero tensile strength has a maximum rotational rate determined by the object’s density, not size. Therefore, an iron asteroid with a density of 8000 kg/m^3 would have a minimum spin period of 1.16h if the only forces were gravitational and centrifugal. The short-term goal is to include material forces in the simulations to determine what tensile strength will allow the high spin rates of asteroids smaller than 150m.
Pumping machinery theory and practice
Badr, Hassan M
2014-01-01
Pumping Machinery Theory and Practice comprehensively covers the theoretical foundation and applications of pumping machinery. Key features: Covers characteristics of centrifugal pumps, axial flow pumps and displacement pumpsConsiders pumping machinery performance and operational-type problemsCovers advanced topics in pumping machinery including multiphase flow principles, and two and three-phase flow pumping systemsCovers different methods of flow rate control and relevance to machine efficiency and energy consumptionCovers different methods of flow rate control and relevance to machine effi
Cooney, Adeline
2011-01-01
This paper explores ways to enhance and demonstrate rigour in a grounded theory study. Grounded theory is sometimes criticised for a lack of rigour. Beck (1993) identified credibility, auditability and fittingness as the main standards of rigour for qualitative research methods. These criteria were evaluated for applicability to a Straussian grounded theory study and expanded or refocused where necessary. The author uses a Straussian grounded theory study (Cooney, In press) to examine how the revised criteria can be applied when conducting a grounded theory study. Strauss and Corbin (1998b) criteria for judging the adequacy of a grounded theory were examined in the context of the wider literature examining rigour in qualitative research studies in general and grounded theory studies in particular. A literature search for 'rigour' and 'grounded theory' was carried out to support this analysis. Criteria are suggested for enhancing and demonstrating the rigour of a Straussian grounded theory study. These include: cross-checking emerging concepts against participants' meanings, asking experts if the theory 'fit' their experiences, and recording detailed memos outlining all analytical and sampling decisions. IMPLICATIONS FOR RESEARCH PRACTICE: The criteria identified have been expressed as questions to enable novice researchers to audit the extent to which they are demonstrating rigour when writing up their studies. However, it should not be forgotten that rigour is built into the grounded theory method through the inductive-deductive cycle of theory generation. Care in applying the grounded theory methodology correctly is the single most important factor in ensuring rigour.
Theories of Career Development. A Comparison of the Theories.
Osipow, Samuel H.
These seven theories of career development are examined in previous chapters: (1) Roe's personality theory, (2) Holland's career typology theory, (3) the Ginzberg, Ginsburg, Axelrod, and Herma Theory, (4) psychoanalytic conceptions, (5) Super's developmental self-concept theory, (6) other personality theories, and (7) social systems theories.…
Supersymmetric gauge theories from string theory
International Nuclear Information System (INIS)
Metzger, St.
2005-12-01
This thesis presents various ways to construct four-dimensional quantum field theories from string theory. In a first part we study the generation of a supersymmetric Yang-Mills theory, coupled to an adjoint chiral superfield, from type IIB string theory on non-compact Calabi-Yau manifolds, with D-branes wrapping certain sub-cycles. Properties of the gauge theory are then mapped to the geometric structure of the Calabi-Yau space. Even if the Calabi-Yau geometry is too complicated to evaluate the geometric integrals explicitly, one can then always use matrix model perturbation theory to calculate the effective superpotential. The second part of this work covers the generation of four-dimensional super-symmetric gauge theories, carrying several important characteristic features of the standard model, from compactifications of eleven-dimensional supergravity on G 2 -manifolds. If the latter contain conical singularities, chiral fermions are present in the four-dimensional gauge theory, which potentially lead to anomalies. We show that, locally at each singularity, these anomalies are cancelled by the non-invariance of the classical action through a mechanism called 'anomaly inflow'. Unfortunately, no explicit metric of a compact G 2 -manifold is known. Here we construct families of metrics on compact weak G 2 -manifolds, which contain two conical singularities. Weak G 2 -manifolds have properties that are similar to the ones of proper G 2 -manifolds, and hence the explicit examples might be useful to better understand the generic situation. Finally, we reconsider the relation between eleven-dimensional supergravity and the E 8 x E 8 -heterotic string. This is done by carefully studying the anomalies that appear if the supergravity theory is formulated on a ten-manifold times the interval. Again we find that the anomalies cancel locally at the boundaries of the interval through anomaly inflow, provided one suitably modifies the classical action. (author)
Henneaux, Marc; Vasiliev, Mikhail A
2017-01-01
Symmetries play a fundamental role in physics. Non-Abelian gauge symmetries are the symmetries behind theories for massless spin-1 particles, while the reparametrization symmetry is behind Einstein's gravity theory for massless spin-2 particles. In supersymmetric theories these particles can be connected also to massless fermionic particles. Does Nature stop at spin-2 or can there also be massless higher spin theories. In the past strong indications have been given that such theories do not exist. However, in recent times ways to evade those constraints have been found and higher spin gauge theories have been constructed. With the advent of the AdS/CFT duality correspondence even stronger indications have been given that higher spin gauge theories play an important role in fundamental physics. All these issues were discussed at an international workshop in Singapore in November 2015 where the leading scientists in the field participated. This volume presents an up-to-date, detailed overview of the theories i...
Covariant Noncommutative Field Theory
Energy Technology Data Exchange (ETDEWEB)
Estrada-Jimenez, S [Licenciaturas en Fisica y en Matematicas, Facultad de Ingenieria, Universidad Autonoma de Chiapas Calle 4a Ote. Nte. 1428, Tuxtla Gutierrez, Chiapas (Mexico); Garcia-Compean, H [Departamento de Fisica, Centro de Investigacion y de Estudios Avanzados del IPN P.O. Box 14-740, 07000 Mexico D.F., Mexico and Centro de Investigacion y de Estudios Avanzados del IPN, Unidad Monterrey Via del Conocimiento 201, Parque de Investigacion e Innovacion Tecnologica (PIIT) Autopista nueva al Aeropuerto km 9.5, Lote 1, Manzana 29, cp. 66600 Apodaca Nuevo Leon (Mexico); Obregon, O [Instituto de Fisica de la Universidad de Guanajuato P.O. Box E-143, 37150 Leon Gto. (Mexico); Ramirez, C [Facultad de Ciencias Fisico Matematicas, Universidad Autonoma de Puebla, P.O. Box 1364, 72000 Puebla (Mexico)
2008-07-02
The covariant approach to noncommutative field and gauge theories is revisited. In the process the formalism is applied to field theories invariant under diffeomorphisms. Local differentiable forms are defined in this context. The lagrangian and hamiltonian formalism is consistently introduced.
Zielenkiewicz, Wojciech
2004-01-01
The purpose of this book is to give a comprehensive description of the theoretical fundamentals of calorimetry. The considerations are based on the relations deduced from the laws and general equations of heat exchange theory and steering theory.
Covariant Noncommutative Field Theory
International Nuclear Information System (INIS)
Estrada-Jimenez, S.; Garcia-Compean, H.; Obregon, O.; Ramirez, C.
2008-01-01
The covariant approach to noncommutative field and gauge theories is revisited. In the process the formalism is applied to field theories invariant under diffeomorphisms. Local differentiable forms are defined in this context. The lagrangian and hamiltonian formalism is consistently introduced
Stabilizing bottomless action theories
International Nuclear Information System (INIS)
Greensite, J.; Halpern, M.B.
1983-12-01
The authors show how to construct the Euclidean quantum theory corresponding to classical actions which are unbounded from below. The method preserves the classical limit, the large-N limit, and the perturbative expansion of the unstabilized theories. (Auth.)
Algebraic conformal field theory
International Nuclear Information System (INIS)
Fuchs, J.; Nationaal Inst. voor Kernfysica en Hoge-Energiefysica
1991-11-01
Many conformal field theory features are special versions of structures which are present in arbitrary 2-dimensional quantum field theories. So it makes sense to describe 2-dimensional conformal field theories in context of algebraic theory of superselection sectors. While most of the results of the algebraic theory are rather abstract, conformal field theories offer the possibility to work out many formulae explicitly. In particular, one can construct the full algebra A-bar of global observables and the endomorphisms of A-bar which represent the superselection sectors. Some explicit results are presented for the level 1 so(N) WZW theories; the algebra A-bar is found to be the enveloping algebra of a Lie algebra L-bar which is an extension of the chiral symmetry algebra of the WZW theory. (author). 21 refs., 6 figs
Rothbart, Andrea
2012-01-01
An imaginative introduction to number theory and abstract algebra, this unique approach employs a pair of fictional characters whose dialogues explain theories and demonstrate applications in terms of football scoring, chess moves, and more.
Economic theories of dictatorship
Alexandre Debs
2010-01-01
This article reviews recent advances in economic theories of dictatorships and their lessons for the political stability and economic performance of dictatorships. It reflects on the general usefulness of economic theories of dictatorship, with an application to foreign relations.
International Nuclear Information System (INIS)
Elliott, J.A.
1993-01-01
Plasma kinetic theory is discussed and a comparison made with the kinetic theory of gases. The plasma is described by a modified set of fluid equations and it is shown how these fluid equations can be derived. (UK)
Indian Academy of Sciences (India)
strongly motivate a detailed search for inflation within string theory, although it has ... between string theory and observations provides a strong incentive for ..... sonably be expected to arise for any system having very many degrees of freedom.
International Nuclear Information System (INIS)
Bonara, L.; Cotta-Ramusino, P.; Rinaldi, M.
1987-01-01
It is well-known that type I and heterotic superstring theories have a zero mass spectrum which correspond to the field content of N=1 supergravity theory coupled to supersymmetric Yang-Mills theory in 10-D. The authors study the field theory ''per se'', in the hope that simple consistency requirements will determine the theory completely once one knows the field content inherited from string theory. The simplest consistency requirements are: N=1 supersymmetry; and absence of chiral anomalies. This is what the authors discuss in this paper here leaving undetermined the question of the range of validity of the resulting field theory. As is known, a model of N=1 supergravity (SUGRA) coupled to supersymmetric Yang-Mills (SYM) theory was known in the form given by Chapline and Manton. The coupling of SUGRA to SYM was determined by the definition of the ''field strength'' 3-form H in this paper
Introduction to percolation theory
Stauffer, Dietrich
1991-01-01
Percolation theory deals with clustering, criticallity, diffusion, fractals, phase transitions and disordered systems. This book covers the basic theory for the graduate, and also professionals dealing with it for the first time
DEFF Research Database (Denmark)
Clemmensen, Torkil; Kaptelinin, Victor; Nardi, Bonnie
2016-01-01
different ways of using activity theory: (1) analysing unique features, principles, and problematic aspects of the theory; (2) identifying domain-specific requirements for new theoretical tools; (3) developing new conceptual accounts of issues in the field of HCI; (4) guiding and supporting empirical...... analyses of HCI phenomena; and (5) providing new design illustrations, claims, and guidelines. We conclude that HCI researchers are not only users of imported theory, but also theory-makers who adapt and develop theory for different purposes.......This paper reports a study of the use of activity theory in human–computer interaction (HCI) research. We analyse activity theory in HCI since its first appearance about 25 years ago. Through an analysis and meta-synthesis of 109 selected HCI activity theory papers, we created a taxonomy of 5...
International Nuclear Information System (INIS)
Partovi, M.H.
1982-01-01
From a generalization of the covariant derivative, nonlocal gauge theories are developed. These theories enjoy local gauge invariance and associated Ward identities, a corresponding locally conserved current, and a locally conserved energy-momentum tensor, with the Ward identities implying the masslessness of the gauge field as in local theories. Their ultraviolet behavior allows the presence as well as the absence of the Adler-Bell-Jackiw anomaly, the latter in analogy with lattice theories
International Nuclear Information System (INIS)
Douglas, Michael R.; Nekrasov, Nikita A.
2001-01-01
This article reviews the generalization of field theory to space-time with noncommuting coordinates, starting with the basics and covering most of the active directions of research. Such theories are now known to emerge from limits of M theory and string theory and to describe quantum Hall states. In the last few years they have been studied intensively, and many qualitatively new phenomena have been discovered, on both the classical and the quantum level
International Nuclear Information System (INIS)
Adler, S.L.; Wilczek, F.
1993-11-01
Areas of emphasis include acceleration algorithms for the Monte Carlo analysis of lattice field and gauge theories, quaternionic generalizations of complex quantum mechanics and field theory, application of the renormalization group to the QCD phase transition, the quantum Hall effect, and black holes. Other work involved string theory, statistical properties of energy levels in integrable quantum systems, baryon asymmetry and the electroweak phase transition, anisotropies of the cosmic microwave background, and theory of superconductors
1990-02-21
LIDS-P-1953 Multiscale System Theory Albert Benveniste IRISA-INRIA, Campus de Beaulieu 35042 RENNES CEDEX, FRANCE Ramine Nikoukhah INRIA...TITLE AND SUBTITLE Multiscale System Theory 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...the development of a corresponding system theory and a theory of stochastic processes and their estimation. The research presented in this and several
Philosophical theories of probability
Gillies, Donald
2000-01-01
The Twentieth Century has seen a dramatic rise in the use of probability and statistics in almost all fields of research. This has stimulated many new philosophical ideas on probability. Philosophical Theories of Probability is the first book to present a clear, comprehensive and systematic account of these various theories and to explain how they relate to one another. Gillies also offers a distinctive version of the propensity theory of probability, and the intersubjective interpretation, which develops the subjective theory.
Davis, Philip W.
This volume explores objectively the essential characteristic of nine twentieth-century linguistic theories with the theoretical variant for discussion based on one closely representative of work within a given approach or usually associated with the name of the theory. First, the theory of Ferdinand de Saussure is discussed based on his book,…
Constructivist Grounded Theory?
Directory of Open Access Journals (Sweden)
Barney G. Glaser, PhD, Hon. PhD
2012-06-01
Full Text Available AbstractI refer to and use as scholarly inspiration Charmaz’s excellent article on constructivist grounded theory as a tool of getting to the fundamental issues on why grounded theory is not constructivist. I show that constructivist data, if it exists at all, is a very, very small part of the data that grounded theory uses.
Maasland, E.
2012-01-01
Auction theory is a branch of game theory that considers human behavior in auction markets and the ensuing market outcomes. It is also successfully used as a tool to design real-life auctions. This thesis contains five essays addressing a variety of topics within the realm of auction theory. The
International Nuclear Information System (INIS)
Prasad, R.
1975-01-01
Results of researches into Unified Field Theory over the past seven years are presented. The subject is dealt with in chapters entitled: the choice of affine connection, algebraic properties of the vector fields, field laws obtained from the affine connection based on the path integral method, application to quantum theory and cosmology, interpretation of physical theory in terms of geometry. (U.K.)
Missinne, Leo E.; Wilcox, Victoria
This paper discusses the life, theories, and therapeutic techniques of psychotherapist, Viktor E. Frankl. A brief biography of Frankl is included discussing the relationship of his early experiences as a physician to his theory of personality. Frankl's theory focusing on man's need for meaning and emphasizing the spiritual dimension in each human…
Rajendran, Gnanathusharan; Mitchell, Peter
2007-01-01
This article considers three theories of autism: The Theory of Mind Deficit, Executive Dysfunction and the Weak Central Coherence accounts. It outlines each along with studies relevant to their emergence, their expansion, their limitations and their possible integration. Furthermore, consideration is given to any implication from the theories in…
International Nuclear Information System (INIS)
Mack, G.
1982-01-01
After a description of a pure Yang-Mills theory on a lattice, the author considers a three-dimensional pure U(1) lattice gauge theory. Thereafter he discusses the exact relation between lattice gauge theories with the gauge groups SU(2) and SO(3). Finally he presents Monte Carlo data on phase transitions in SU(2) and SO(3) lattice gauge models. (HSI)
Onderstal, A.M.
2002-01-01
This thesis is a collection of six papers in auction theory, with several economic applications, both to real life auctions and to other economic phenomena. In the introduction to the thesis, Onderstal argues why auction theory is an important branch of economic theory, and discusses several
Vazzana, Anthony; Garth, David
2007-01-01
One of the oldest branches of mathematics, number theory is a vast field devoted to studying the properties of whole numbers. Offering a flexible format for a one- or two-semester course, Introduction to Number Theory uses worked examples, numerous exercises, and two popular software packages to describe a diverse array of number theory topics.
Reflections on Activity Theory
Bakhurst, David
2009-01-01
It is sometimes suggested that activity theory represents the most important legacy of Soviet philosophy and psychology. But what exactly "is" activity theory? The canonical account in the West is given by Engestrom, who identifies three stages in the theory's development: from Vygotsky's insights, through Leontiev's articulation of the…
Superspace conformal field theory
Energy Technology Data Exchange (ETDEWEB)
Quella, Thomas [Koeln Univ. (Germany). Inst. fuer Theoretische Physik; Schomerus, Volker [Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
2013-07-15
Conformal sigma models and WZW models on coset superspaces provide important examples of logarithmic conformal field theories. They possess many applications to problems in string and condensed matter theory. We review recent results and developments, including the general construction of WZW models on type I supergroups, the classification of conformal sigma models and their embedding into string theory.
Superspace conformal field theory
International Nuclear Information System (INIS)
Quella, Thomas
2013-07-01
Conformal sigma models and WZW models on coset superspaces provide important examples of logarithmic conformal field theories. They possess many applications to problems in string and condensed matter theory. We review recent results and developments, including the general construction of WZW models on type I supergroups, the classification of conformal sigma models and their embedding into string theory.
International Nuclear Information System (INIS)
Kikkawa, Keiji; Nakanishi, Noboru; Nariai, Hidekazu
1983-01-01
These proceedings contain the articles presented at the named symposium. They deal with geometrical aspects of gauge theory and gravitation, special problems in gauge theories, quantum field theory in curved space-time, quantum gravity, supersymmetry including supergravity, and grand unification. See hints under the relevant topics. (HSI)
Constructor theory of probability
2016-01-01
Unitary quantum theory, having no Born Rule, is non-probabilistic. Hence the notorious problem of reconciling it with the unpredictability and appearance of stochasticity in quantum measurements. Generalizing and improving upon the so-called ‘decision-theoretic approach’, I shall recast that problem in the recently proposed constructor theory of information—where quantum theory is represented as one of a class of superinformation theories, which are local, non-probabilistic theories conforming to certain constructor-theoretic conditions. I prove that the unpredictability of measurement outcomes (to which constructor theory gives an exact meaning) necessarily arises in superinformation theories. Then I explain how the appearance of stochasticity in (finitely many) repeated measurements can arise under superinformation theories. And I establish sufficient conditions for a superinformation theory to inform decisions (made under it) as if it were probabilistic, via a Deutsch–Wallace-type argument—thus defining a class of decision-supporting superinformation theories. This broadens the domain of applicability of that argument to cover constructor-theory compliant theories. In addition, in this version some of the argument's assumptions, previously construed as merely decision-theoretic, follow from physical properties expressed by constructor-theoretic principles. PMID:27616914
Schmidt, Ulrich; Zank, Horst
2010-01-01
In previous models of (cumulative) prospect theory reference-dependence of preferences is imposed beforehand and the location of the reference point is exogenously determined. This paper provides an axiomatization of a new specification of cumulative prospect theory, termed endogenous prospect theory, where reference-dependence is derived from preference conditions and a unique reference point arises endogenously.
Sharpening Intertemporal Prospect Theory
Pushpa, Rathie; Carlos, Radavelli; Sergio, Da Silva
2006-01-01
Prospect theory [4] of risky choices has been extended to encompass intertemporal choices [6]. Presentation of intertemporal prospect theory suffers from minor mistakes, however [2]. To clarify the theory we restate it and show further mistakes in current presentations ([6], [2]) of value and discount functions.
On the relation between gene flow theory and genetic gain
Directory of Open Access Journals (Sweden)
Woolliams John A
2000-01-01
Full Text Available Abstract In conventional gene flow theory the rate of genetic gain is calculated as the summed products of genetic selection differential and asymptotic proportion of genes deriving from sex-age groups. Recent studies have shown that asymptotic proportions of genes predicted from conventional gene flow theory may deviate considerably from true proportions. However, the rate of genetic gain predicted from conventional gene flow theory was accurate. The current note shows that the connection between asymptotic proportions of genes and rate of genetic gain that is embodied in conventional gene flow theory is invalid, even though genetic gain may be predicted correctly from it.
Gauge theories as theories of spontaneous breakdown
International Nuclear Information System (INIS)
Ivanov, E.A.; Ogievetsky, V.I.
1976-01-01
Any gauge theory is proved to arise from spontaneous breakdown of symmetry under certain infinite parameter group, the corresponding gauge field being the Goldstone field by which this breakdown is accompanied
Theory and context / Theory in context
DEFF Research Database (Denmark)
Glaveanu, Vlad Petre
2014-01-01
trans-disciplinary manner. Consideration needs to be given as well to connected scholarship focusing on imagination, innova-tion, and improvisation. Last but not least, an expanded the-ory of context cannot ignore the institutional context of doing research on creativity. Creativity scholars are facing......It is debatable whether the psychology of creativity is a field in crisis or not. There are clear signs of increased fragmenta-tion and a scarcity of integrative efforts, but is this necessari-ly bad? Do we need more comprehensive theories of creativ-ity and a return to old epistemological...... questions? This de-pends on how one understands theory. Against a view of theoretical work as aiming towards generality, universality, uniformity, completeness, and singularity, I advocate for a dynamic perspective in which theory is plural, multifaceted, and contextual. Far from ‘waiting for the Messiah...
Invariant Theory (IT) & Standard Monomial Theory (SMT)
Indian Academy of Sciences (India)
2013-07-06
Jul 6, 2013 ... Why invariant theory? (continued). Now imagine algebraic calculations being made, with the two different sets of co-ordinates, about something of geometrical or physical interest concerning the configuration of points, ...
Reaction rate of propene pyrolysis.
Han, Peipei; Su, Kehe; Liu, Yan; Wang, Yanli; Wang, Xin; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong
2011-10-01
The reaction rate of propene pyrolysis was investigated based on the elementary reactions proposed in Qu et al., J Comput Chem 2009, 31, 1421. The overall reaction rate was developed with the steady-state approximation and the rate constants of the elementary reactions were determined with the variational transition state theory. For the elementary reaction having transition state, the vibrational frequencies of the selected points along the minimum energy path were calculated with density functional theory at B3PW91/6-311G(d,p) level and the energies were improved with the accurate model chemistry method G3(MP2). For the elementary reaction without transition state, the frequencies were calculated with CASSCF/6-311G(d,p) and the energies were refined with the multireference configuration interaction method MRCISD/6-311G(d,p). The rate constants were evaluated within 200-2000 K and the fitted three-parameter expressions were obtained. The results are consistent with those in the literatures in most cases. For the overall rate, it was found that the logarithm of the rate and the reciprocal temperature have excellent linear relationship above 400 K, predicting that the rate follows a typical first-order law at high temperatures of 800-2000 K, which is also consistent with the experiments. The apparent activation energy in 800-2000 K is 317.3 kJ/mol from the potential energy surface of zero Kelvin. This value is comparable with the energy barriers, 365.4 and 403.7 kJ/mol, of the rate control steps. However, the apparent activation energy, 215.7 kJ/mol, developed with the Gibbs free energy surface at 1200 K is consistent with the most recent experimental result 201.9 ± 0.6 kJ/mol. Copyright © 2011 Wiley Periodicals, Inc.
Irvine, J M
1972-01-01
Nuclear Structure Theory provides a guide to nuclear structure theory. The book is comprised of 23 chapters that are organized into four parts; each part covers an aspect of nuclear structure theory. In the first part, the text discusses the experimentally observed phenomena, which nuclear structure theories need to look into and detail the information that supports those theories. The second part of the book deals with the phenomenological nucleon-nucleon potentials derived from phase shift analysis of nucleon-nucleon scattering. Part III talks about the phenomenological parameters used to de
Measure and integration theory
Burckel, Robert B
2001-01-01
This book gives a straightforward introduction to the field as it is nowadays required in many branches of analysis and especially in probability theory. The first three chapters (Measure Theory, Integration Theory, Product Measures) basically follow the clear and approved exposition given in the author's earlier book on ""Probability Theory and Measure Theory"". Special emphasis is laid on a complete discussion of the transformation of measures and integration with respect to the product measure, convergence theorems, parameter depending integrals, as well as the Radon-Nikodym theorem. The fi
Kilmister, Clive William
1970-01-01
Special Theory of Relativity provides a discussion of the special theory of relativity. Special relativity is not, like other scientific theories, a statement about the matter that forms the physical world, but has the form of a condition that the explicit physical theories must satisfy. It is thus a form of description, playing to some extent the role of the grammar of physics, prescribing which combinations of theoretical statements are admissible as descriptions of the physical world. Thus, to describe it, one needs also to describe those specific theories and to say how much they are limit
Bollobas, Bela
2004-01-01
The ever-expanding field of extremal graph theory encompasses a diverse array of problem-solving methods, including applications to economics, computer science, and optimization theory. This volume, based on a series of lectures delivered to graduate students at the University of Cambridge, presents a concise yet comprehensive treatment of extremal graph theory.Unlike most graph theory treatises, this text features complete proofs for almost all of its results. Further insights into theory are provided by the numerous exercises of varying degrees of difficulty that accompany each chapter. A
Introduction to spectral theory
Levitan, B M
1975-01-01
This monograph is devoted to the spectral theory of the Sturm- Liouville operator and to the spectral theory of the Dirac system. In addition, some results are given for nth order ordinary differential operators. Those parts of this book which concern nth order operators can serve as simply an introduction to this domain, which at the present time has already had time to become very broad. For the convenience of the reader who is not familar with abstract spectral theory, the authors have inserted a chapter (Chapter 13) in which they discuss this theory, concisely and in the main without proofs, and indicate various connections with the spectral theory of differential operators.
Barron, E N
2013-01-01
An exciting new edition of the popular introduction to game theory and its applications The thoroughly expanded Second Edition presents a unique, hands-on approach to game theory. While most books on the subject are too abstract or too basic for mathematicians, Game Theory: An Introduction, Second Edition offers a blend of theory and applications, allowing readers to use theory and software to create and analyze real-world decision-making models. With a rigorous, yet accessible, treatment of mathematics, the book focuses on results that can be used to
Prest, M
1988-01-01
In recent years the interplay between model theory and other branches of mathematics has led to many deep and intriguing results. In this, the first book on the topic, the theme is the interplay between model theory and the theory of modules. The book is intended to be a self-contained introduction to the subject and introduces the requisite model theory and module theory as it is needed. Dr Prest develops the basic ideas concerning what can be said about modules using the information which may be expressed in a first-order language. Later chapters discuss stability-theoretic aspects of module
International Nuclear Information System (INIS)
Lucha, W.; Neufeld, H.
1986-01-01
We investigate the relation between finiteness of a four-dimensional quantum field theory and global supersymmetry. To this end we consider the most general quantum field theory and analyse the finiteness conditions resulting from the requirement of the absence of divergent contributions to the renormalizations of the parameters of the theory. In addition to the gauge bosons, both fermions and scalar bosons turn out to be a necessary ingredient in a non-trivial finite gauge theory. In all cases discussed, the supersymmetric theory restricted by two well-known constraints on the dimensionless couplings proves to be the unique solution of the finiteness conditions. (Author)
Smith’s theory of wages and its impact on the theory of wages in the 19th century
Directory of Open Access Journals (Sweden)
Stojanović Božo
2005-01-01
Full Text Available Adam Smith has not accepted subsistence theory of wages as an explanation of wages. He can be marked not only as a founder of wages-fund theory, but also of the bargaining theory of wages. Wage-fund doctrine dominated the next hundred years of English economics. Besides, Smith’s explanation of the differentials in wage rates among occupations were accepted by his successors for a century. That was the first step into direction of human capital theory.
International Nuclear Information System (INIS)
Eloranta, E.
2003-11-01
The geophysical field theory includes the basic principles of electromagnetism, continuum mechanics, and potential theory upon which the computational modelling of geophysical phenomena is based on. Vector analysis is the main mathematical tool in the field analyses. Electrostatics, stationary electric current, magnetostatics, and electrodynamics form a central part of electromagnetism in geophysical field theory. Potential theory concerns especially gravity, but also electrostatics and magnetostatics. Solid state mechanics and fluid mechanics are central parts in continuum mechanics. Also the theories of elastic waves and rock mechanics belong to geophysical solid state mechanics. The theories of geohydrology and mass transport form one central field theory in geophysical fluid mechanics. Also heat transfer is included in continuum mechanics. (orig.)
International Nuclear Information System (INIS)
Crisan, M.
1988-01-01
This book discusses the most important aspects of the theory. The phenomenological model is followed by the microscopic theory of superconductivity, in which modern formalism of the many-body theory is used to treat most important problems such as superconducting alloys, coexistence of superconductivity with the magnetic order, and superconductivity in quasi-one-dimensional systems. It concludes with a discussion on models for exotic and high temperature superconductivity. Its main aim is to review, as complete as possible, the theory of superconductivity from classical models and methods up to the 1987 results on high temperature superconductivity. Contents: Phenomenological Theory of Superconductivity; Microscopic Theory of Superconductivity; Theory of Superconducting Alloys; Superconductors in a Magnetic Field; Superconductivity and Magnetic Order; Superconductivity in Quasi-One-Dimensional Systems; and Non-Conventional Superconductivity
International Nuclear Information System (INIS)
Yilmaz, H.
1975-01-01
Schwinger's source theory is applied to the problem of gravitation and its quantization. It is shown that within the framework of a flat-space the source theory implementation leads to a violation of probability. To avoid the difficulty one must introduce a curved space-time hence the source concept may be said to necessitate the transition to a curved-space theory of gravitation. It is further shown that the curved-space theory of gravitation implied by the source theory is not equivalent to the conventional Einstein theory. The source concept leads to a different theory where the gravitational field has a stress-energy tensor t/sup nu//sub mu/ which contributes to geometric curvatures
Introduction to representation theory
Etingof, Pavel; Hensel, Sebastian; Liu, Tiankai; Schwendner, Alex
2011-01-01
Very roughly speaking, representation theory studies symmetry in linear spaces. It is a beautiful mathematical subject which has many applications, ranging from number theory and combinatorics to geometry, probability theory, quantum mechanics, and quantum field theory. The goal of this book is to give a "holistic" introduction to representation theory, presenting it as a unified subject which studies representations of associative algebras and treating the representation theories of groups, Lie algebras, and quivers as special cases. Using this approach, the book covers a number of standard topics in the representation theories of these structures. Theoretical material in the book is supplemented by many problems and exercises which touch upon a lot of additional topics; the more difficult exercises are provided with hints. The book is designed as a textbook for advanced undergraduate and beginning graduate students. It should be accessible to students with a strong background in linear algebra and a basic k...
[Introduction to grounded theory].
Wang, Shou-Yu; Windsor, Carol; Yates, Patsy
2012-02-01
Grounded theory, first developed by Glaser and Strauss in the 1960s, was introduced into nursing education as a distinct research methodology in the 1970s. The theory is grounded in a critique of the dominant contemporary approach to social inquiry, which imposed "enduring" theoretical propositions onto study data. Rather than starting from a set theoretical framework, grounded theory relies on researchers distinguishing meaningful constructs from generated data and then identifying an appropriate theory. Grounded theory is thus particularly useful in investigating complex issues and behaviours not previously addressed and concepts and relationships in particular populations or places that are still undeveloped or weakly connected. Grounded theory data analysis processes include open, axial and selective coding levels. The purpose of this article was to explore the grounded theory research process and provide an initial understanding of this methodology.
Niederreiter, Harald
2015-01-01
This textbook effectively builds a bridge from basic number theory to recent advances in applied number theory. It presents the first unified account of the four major areas of application where number theory plays a fundamental role, namely cryptography, coding theory, quasi-Monte Carlo methods, and pseudorandom number generation, allowing the authors to delineate the manifold links and interrelations between these areas. Number theory, which Carl-Friedrich Gauss famously dubbed the queen of mathematics, has always been considered a very beautiful field of mathematics, producing lovely results and elegant proofs. While only very few real-life applications were known in the past, today number theory can be found in everyday life: in supermarket bar code scanners, in our cars’ GPS systems, in online banking, etc. Starting with a brief introductory course on number theory in Chapter 1, which makes the book more accessible for undergraduates, the authors describe the four main application areas in Chapters...
Computational invariant theory
Derksen, Harm
2015-01-01
This book is about the computational aspects of invariant theory. Of central interest is the question how the invariant ring of a given group action can be calculated. Algorithms for this purpose form the main pillars around which the book is built. There are two introductory chapters, one on Gröbner basis methods and one on the basic concepts of invariant theory, which prepare the ground for the algorithms. Then algorithms for computing invariants of finite and reductive groups are discussed. Particular emphasis lies on interrelations between structural properties of invariant rings and computational methods. Finally, the book contains a chapter on applications of invariant theory, covering fields as disparate as graph theory, coding theory, dynamical systems, and computer vision. The book is intended for postgraduate students as well as researchers in geometry, computer algebra, and, of course, invariant theory. The text is enriched with numerous explicit examples which illustrate the theory and should be ...
DEFF Research Database (Denmark)
Wæver, Ole
2011-01-01
theory is found to ‘act politically’ through three structural features that systematically shape the political effects of using the theory. The article further discusses – on the basis of the preceding articles in the special issue – three emerging debates around securitization theory: ethics......This article outlines three ways of analysing the ‘politics of securitization’, emphasizing an often-overlooked form of politics practised through theory design. The structure and nature of a theory can have systematic political implications. Analysis of this ‘politics of securitization......’ is distinct from both the study of political practices of securitization and explorations of competing concepts of politics among security theories. It means tracking what kinds of analysis the theory can produce and whether such analysis systematically impacts real-life political struggles. Securitization...
Kim, E.; Newton, A. P.
2012-04-01
One major problem in dynamo theory is the multi-scale nature of the MHD turbulence, which requires statistical theory in terms of probability distribution functions. In this contribution, we present the statistical theory of magnetic fields in a simplified mean field α-Ω dynamo model by varying the statistical property of alpha, including marginal stability and intermittency, and then utilize observational data of solar activity to fine-tune the mean field dynamo model. Specifically, we first present a comprehensive investigation into the effect of the stochastic parameters in a simplified α-Ω dynamo model. Through considering the manifold of marginal stability (the region of parameter space where the mean growth rate is zero), we show that stochastic fluctuations are conductive to dynamo. Furthermore, by considering the cases of fluctuating alpha that are periodic and Gaussian coloured random noise with identical characteristic time-scales and fluctuating amplitudes, we show that the transition to dynamo is significantly facilitated for stochastic alpha with random noise. Furthermore, we show that probability density functions (PDFs) of the growth-rate, magnetic field and magnetic energy can provide a wealth of useful information regarding the dynamo behaviour/intermittency. Finally, the precise statistical property of the dynamo such as temporal correlation and fluctuating amplitude is found to be dependent on the distribution the fluctuations of stochastic parameters. We then use observations of solar activity to constrain parameters relating to the effect in stochastic α-Ω nonlinear dynamo models. This is achieved through performing a comprehensive statistical comparison by computing PDFs of solar activity from observations and from our simulation of mean field dynamo model. The observational data that are used are the time history of solar activity inferred for C14 data in the past 11000 years on a long time scale and direct observations of the sun spot
The Determinants of Country Risk Ratings
Jean-Claude Cosset; Jean Roy
1991-01-01
The purpose of this paper is to replicate Euromoney's and Institutional Investor's country risk ratings on the basis of economic and political variables. The evidence reveals that country risk ratings respond to some of the variables suggested by the theory. In particular, both the level of per capita income and propensity to invest affect positively the rating of a country. In addition, high-ranking countries are less indebted than low-ranking countries. It also appears that the ability of t...
International Nuclear Information System (INIS)
Meyna, A.
1982-01-01
After a general introduction to safety theory, safety characteristics are defined and quantified. This is followed by a calculation of the safety characteristics of simple, safety-relevant systems in general and in consideration of common-mode errors. The qualitative and quantitative role of human errors is discussed for various models, and a simple man-machine model is developed for investigation of common-mode errors and human error. The main part of the paper deals with safety analysis in complex systems. After a general review, the common inductive and deductive methods of analysis are presented and commented on and their fields of application discussed. Analytical and simulation codes are presented as methods of evaluation for big, complex event trees - i.e. ''hazard trees in the sense of safety engineering (as a subset of safety relevance). After a basic classification and mathematical formulation of Markovian processes, the author shows that these may be used successfully for calculation of safety characteristics if transition rates are constant and if the number of system states is limited. (orig./RW) [de
International Nuclear Information System (INIS)
Anchordoqui, Luis; Nawata, Satoshi; Goldberg, Haim; Nunez, Carlos
2007-01-01
We explore the cosmological content of Salam-Sezgin six-dimensional supergravity, and find a solution to the field equations in qualitative agreement with observation of distant supernovae, primordial nucleosynthesis abundances, and recent measurements of the cosmic microwave background. The carrier of the acceleration in the present de Sitter epoch is a quintessence field slowly rolling down its exponential potential. Intrinsic to this model is a second modulus which is automatically stabilized and acts as a source of cold dark matter, with a mass proportional to an exponential function of the quintessence field (hence realizing varying mass particle models within a string context). However, any attempt to saturate the present cold dark matter component in this manner leads to unacceptable deviations from cosmological data--a numerical study reveals that this source can account for up to about 7% of the total cold dark matter budget. We also show that (1) the model will support a de Sitter energy in agreement with observation at the expense of a miniscule breaking of supersymmetry in the compact space; (2) variations in the fine structure constant are controlled by the stabilized modulus and are negligible; (3) ''fifth'' forces are carried by the stabilized modulus and are short range; (4) the long time behavior of the model in four dimensions is that of a Robertson-Walker universe with a constant expansion rate (w=-1/3). Finally, we present a string theory background by lifting our six-dimensional cosmological solution to ten dimensions
Microcanonical quantum field theory
International Nuclear Information System (INIS)
Strominger, A.
1983-01-01
Euclidean quantum field theory is equivalent to the equilibrium statistical mechanics of classical fields in 4+1 dimensions at temperature h. It is well known in statistical mechanics that the theory of systems at fixed temperature is embedded within the more general and fundamental theory of systems at fixed energy. We therefore develop, in precise analogy, a fixed action (macrocanonical) formulation of quantum field theory. For the case of ordinary renormalizable field theories, we show (with one exception) that the microcanonical is entirely equivalent to the canonical formulation. That is, for some particular fixed value of the total action, the Green's functions of the microcanonical theory are equal, in the bulk limit, to those of the canonical theory. The microcanonical perturbation expansion is developed in some detail for lambdaphi 4 . The particular value of the action for which the two formulations are equivalent can be calculated to all orders in perturbation theory. We prove, using Lehmann's Theorem, that this value is one-half Planck unit per degree of freedom, if fermionic degrees of freedom are counted negatively. This is the 4+1 dimensional analog of the equipartition theorem. The one exception to this is supersymmetric theories. A microcanonical formulation exists if and only if supersymmetry is broken. In statistical mechanics and in field theory there are systems for which the canonical description is pathological, but the microcanonical is not. An example of such a field theory is found in one dimension. A semiclassical expansion of the microcanonical theory is well defined, while an expansion of the canonical theory is hoplessly divergent
Particle physics and gauge theories
International Nuclear Information System (INIS)
Morel, A.
1985-01-01
These notes are intended to help readers not familiar with particle physics in entering the domain of gauge field theory applied to the so-called standard model of strong and electroweak interactions. The introduction is considerably enlarged in order to give non specialists a general overview of present days ''elementary'' particle physics. The Glashow-Salam-Weinberg model is then treated, with the details which its unquestioned successes deserve, most probably for a long time. Finally SU(5) is presented as a prototype of these developments of particle physics which aim at a unification of all forces. Although its intrinsic theoretical difficulties and the non-observation of a sizable proton decay rate do not qualify this model as a realistic one, it has many of the properties expected from a ''good'' unified theory. In particular, it allows one to study interesting connections between particle physics and cosmology. 35 refs.
Franklin, Joel
2017-01-01
Classical field theory, which concerns the generation and interaction of fields, is a logical precursor to quantum field theory, and can be used to describe phenomena such as gravity and electromagnetism. Written for advanced undergraduates, and appropriate for graduate level classes, this book provides a comprehensive introduction to field theories, with a focus on their relativistic structural elements. Such structural notions enable a deeper understanding of Maxwell's equations, which lie at the heart of electromagnetism, and can also be applied to modern variants such as Chern–Simons and Born–Infeld. The structure of field theories and their physical predictions are illustrated with compelling examples, making this book perfect as a text in a dedicated field theory course, for self-study, or as a reference for those interested in classical field theory, advanced electromagnetism, or general relativity. Demonstrating a modern approach to model building, this text is also ideal for students of theoretic...
Algebraic quantum field theory
International Nuclear Information System (INIS)
Foroutan, A.
1996-12-01
The basic assumption that the complete information relevant for a relativistic, local quantum theory is contained in the net structure of the local observables of this theory results first of all in a concise formulation of the algebraic structure of the superselection theory and an intrinsic formulation of charge composition, charge conjugation and the statistics of an algebraic quantum field theory. In a next step, the locality of massive particles together with their spectral properties are wed for the formulation of a selection criterion which opens the access to the massive, non-abelian quantum gauge theories. The role of the electric charge as a superselection rule results in the introduction of charge classes which in term lead to a set of quantum states with optimum localization properties. Finally, the asymptotic observables of quantum electrodynamics are investigated within the framework of algebraic quantum field theory. (author)
DEFF Research Database (Denmark)
Zander, Pär Ola
2014-01-01
theory. The paper concludes that Baudrillard's arguments for abandoning Marxism altogether are problematic and led him away from developing a more finished theory of value. This is unfortunate because it remains a project that may yield interesting insights even in contemporary social theory, not least......Jean Baudrillard outlined a theory of value in his early writings that built on, but also criticized, Marxist concepts of use value and exchange value. In this paper, I use a close reading to delineate the diachronic transition of Baudrillard's writings toward anti-Marxism and (allegedly......) postmodernism, with specific focus on his value theory, in order to understand his own reasons for abandoning his previous position. I then follow the marginal stream of scholars who are making use of the early Baudrillard. I find his value theory promising but still a mere sketch rather than an actual general...
DEFF Research Database (Denmark)
Birkedal, Lars; Bizjak, Aleš; Clouston, Ranald
2016-01-01
This paper improves the treatment of equality in guarded dependent type theory (GDTT), by combining it with cubical type theory (CTT). GDTT is an extensional type theory with guarded recursive types, which are useful for building models of program logics, and for programming and reasoning...... with coinductive types. We wish to implement GDTT with decidable type-checking, while still supporting non-trivial equality proofs that reason about the extensions of guarded recursive constructions. CTT is a variation of Martin-L\\"of type theory in which the identity type is replaced by abstract paths between...... terms. CTT provides a computational interpretation of functional extensionality, is conjectured to have decidable type checking, and has an implemented type-checker. Our new type theory, called guarded cubical type theory, provides a computational interpretation of extensionality for guarded recursive...
Karlin, Anna R
2016-01-01
This book presents a rigorous introduction to the mathematics of game theory without losing sight of the joy of the subject. This is done by focusing on theoretical highlights (e.g., at least six Nobel Prize winning results are developed from scratch) and by presenting exciting connections of game theory to other fields, such as computer science, economics, social choice, biology, and learning theory. Both classical topics, such as zero-sum games, and modern topics, such as sponsored search auctions, are covered. Along the way, beautiful mathematical tools used in game theory are introduced, including convexity, fixed-point theorems, and probabilistic arguments. The book is appropriate for a first course in game theory at either the undergraduate or graduate level, whether in mathematics, economics, computer science, or statistics. Game theory's influence is felt in a wide range of disciplines, and the authors deliver masterfully on the challenge of presenting both the breadth and coherence of its underlying ...
International Nuclear Information System (INIS)
Combes, J.M.
1980-10-01
A complementary approach to the time dependent scattering theory for one-body Schroedinger operators is presented. The stationary theory is concerned with objects of quantum theory like scattering waves and amplitudes. In the more recent abstract stationary theory some generalized form of the Lippman-Schwinger equation plays the basic role. Solving this equation leads to a linear map between generalized eigenfunctions of the perturbed and unperturbed operators. This map is the section at fixed energy of the wave-operator from the time dependent theory. Although the radiation condition does not appears explicitely in this formulation it can be shown to hold a posteriori in a variety of situations thus restoring the link with physical theories
Quantum theory without reduction
International Nuclear Information System (INIS)
Cini, Marcello; Levy-Leblond, J.-M.
1990-01-01
Quantum theory offers a strange, and perhaps unique, case in the history of science. Although research into its roots has provided important results in recent years, the debate goes on. Some theorists argue that quantum theory is weakened by the inclusion of the so called 'reduction of the state vector' in its foundations. Quantum Theory without Reduction presents arguments in favour of quantum theory as a consistent and complete theory without this reduction, and which is capable of explaining all known features of the measurement problem. This collection of invited contributions defines and explores different aspects of this issue, bringing an old debate into a new perspective, and leading to a more satisfying consensus about quantum theory. (author)
DEFF Research Database (Denmark)
Birkedal, Lars; Bizjak, Aleš; Clouston, Ranald
2016-01-01
This paper improves the treatment of equality in guarded dependent type theory (GDTT), by combining it with cubical type theory (CTT). GDTT is an extensional type theory with guarded recursive types, which are useful for building models of program logics, and for programming and reasoning...... with coinductive types. We wish to implement GDTT with decidable type checking, while still supporting non-trivial equality proofs that reason about the extensions of guarded recursive constructions. CTT is a variation of Martin-L\\"of type theory in which the identity type is replaced by abstract paths between...... terms. CTT provides a computational interpretation of functional extensionality, enjoys canonicity for the natural numbers type, and is conjectured to support decidable type-checking. Our new type theory, guarded cubical type theory (GCTT), provides a computational interpretation of extensionality...
DEFF Research Database (Denmark)
Balle, Søren Hattesen
This paper takes its starting point in a short poem by Wallace Stevens from 1917, which incidentally bears the title “Theory”. The poem can be read as a parable of theory, i.e., as something literally ’thrown beside’ theory (cf. OED: “...“). In the philosophical tradition this is also how the style of theory has been figured, that is to say: as something that is incidental to it or just happens to be around as so much paraphernalia. In my reading of Stevens’ poem I shall argue that this is exactly the position from which Stevens takes off when he assumes...... the task of writing a personified portrait of theory. Theory emerges as always beside(s) itself in what constitutes its style, but the poem also suggests that theory’s style is what gives theory both its power and its contingency. Figured as a duchess Theoria is only capable of retaining her power...
Supersymmetric gauge field theories
International Nuclear Information System (INIS)
Slavnov, A.A.
1976-01-01
The paper is dealing with the role of supersymmetric gauge theories in the quantum field theory. Methods of manipulating the theories as well as possibilities of their application in elementary particle physics are presented. In particular, the necessity is explained of a theory in which there is symmetry between Fermi and Bose fields, in other words, of the supersymmetric gauge theory for construction of a scheme for the Higgs particle connecting parameters of scalar mesons with those of the rest fields. The mechanism of supersymmetry breaking is discussed which makes it possible to remain the symmetric procedure of renormalization intact. The above mechanism of spontaneous symmetry breaking is applied to demonstrate possibilities of constructing models of weak and electromagnetic interactions which would be acceptable from the point of view of experiments. It is noted that the supersymmetric gauge theories represent a natural technique for description of vector-like models