Molecular Relaxation in Liquids
Bagchi, Biman
2012-01-01
This book brings together many different relaxation phenomena in liquids under a common umbrella and provides a unified view of apparently diverse phenomena. It aligns recent experimental results obtained with modern techniques with recent theoretical developments. Such close interaction between experiment and theory in this area goes back to the works of Einstein, Smoluchowski, Kramers' and de Gennes. Development of ultrafast laser spectroscopy recently allowed study of various relaxation processes directly in the time domain, with time scales going down to picosecond (ps) and femtosecond (fs
Molecular potentials and relaxation dynamics
The use of empirical pseudopotentials, in evaluating interatomic potentials, provides an inexpensive and convenient method for obtaining highly accurate potential curves and permits the modeling of core-valence correlation, and the inclusion of relativistic effects when these are significant. Recent calculations of the X1Σ+ and a3Σ+ states of LiH, NaH, KH, RbH, and CsH and the X2Σ+ states of their anions are discussed. Pseudopotentials, including core polarization terms, have been used to replace the core electrons, and this has been coupled with the development of compact, higly-optimized basis sets for the corresponding one- and two-electron atoms. Comparisons of the neutral potential curves with experiment and other ab initio calculations show good agreement (within 1000 cm-1 over most of the potential curves) with the difference curves being considerably more accurate. In the method of computer molecular dynamics, the force acting on each particle is the resultant of all interactions with other atoms in the neighborhood and is obtained as the derivative of an effective many-body potential. Exploiting the pseudopotential approach, in obtaining the appropriate potentials may be very fruitful in the future. In the molecular dynamics example considered here, the conventional sum-of-pairwise-interatomic-potentials (SPP) approximation is used with the potentials derived either from experimental spectroscopic data or from Hartree-Fock calculations. The problem is the collisional de-excitation of vibrationally excited molecular hydrogen at an Fe surface. The calculations have been carried out for an initial vibrotational state v = 8, J = 1 and a translational temperature corresponding to a gas temperature of 5000K. Different angles of approach and different initial random impact points on the surface have been selected. For any given collision with the wall, the molecule may pick up or lose vibrotatonal and translational energy
Relaxation oscillations in optically pumped molecular lasers
Lawandy, N. M.; Koepf, G. A.
1980-01-01
The observation of relaxation oscillations in both the (C-13)H3F and (C-12)H3F optically pumped lasers is reported. Expressions are derived for the oscillation frequency and its temperature and pressure dependences using a four-level rate equation model. Excellent agreement between measured frequencies and the theory presented is observed. Models are considered for using this phenomenon to determine the rotational and vibrational relaxation mechanisms of the laser gases.
NMR spin-lattice relaxation in molecular rotor systems
Wzietek, P
2015-01-01
A general expression is derived for the dipolar NMR spin-lattice relaxation rate $1/T_1$ of a system exhibiting Brownian dynamics in a discrete and finite configuration space. It is shown that this approach can be particularly useful to model the proton relaxation rate in molecular rotors.
Accelerating convergence of molecular dynamics-based structural relaxation
Christensen, Asbjørn
2005-01-01
We describe strategies to accelerate the terminal stage of molecular dynamics (MD)based relaxation algorithms, where a large fraction of the computational resources are used. First, we analyze the qualitative and quantitative behavior of the QuickMin family of MD relaxation algorithms and explore...... the influence of spectral properties and dimensionality of the molecular system on the algorithm efficiency. We test two algorithms, the MinMax and Lanczos, for spectral estimation from an MD trajectory, and use this to derive a practical scheme of time step adaptation in MD relaxation algorithms to...
Vďačný, Peter
2015-08-01
The class Litostomatea comprises a diverse assemblage of free-living and endosymbiotic ciliates. To understand diversification dynamic of litostomateans, divergence times of their main groups were estimated with the Bayesian molecular dating, a technique allowing relaxation of molecular clock and incorporation of flexible calibration points. The class Litostomatea very likely emerged during the Cryogenian around 680 Mya. The origin of the subclass Rhynchostomatia is dated to about 415 Mya, while that of the subclass Haptoria to about 654 Mya. The order Pleurostomatida, emerging about 556 Mya, was recognized as the oldest group within the subclass Haptoria. The order Spathidiida appeared in the Paleozoic about 442 Mya. The three remaining haptorian orders evolved in the Paleozoic/Mesozoic periods: Didiniida about 419 Mya, Lacrymariida about 269 Mya, and Haptorida about 194 Mya. The subclass Trichostomatia originated from a spathidiid ancestor in the Mesozoic about 260 Mya. A further goal of this study was to investigate the impact of various settings on posterior divergence time estimates. The root placement and tree topology as well as the priors of the rate-drift model, birth-death process and nucleotide substitution rate, had no significant effect on calculation of posterior divergence time estimates. However, removal of calibration points could significantly change time estimates at some nodes. PMID:26204556
Free-volume hole relaxation in molecularly oriented glassy polymers
Xia, Zhiyong; Trexler, Morgana; Wu, Fei; Jean, Yan-Ching; Van Horn, J. David
2014-02-01
The free-volume hole relaxation in polycarbonate and poly(methyl methacrylate) with different levels of molecular orientation was studied by positron annihilation lifetime spectroscopy at variable pressures. The molecular orientation was achieved through a simple shear process performed at different temperatures and extrusion rates. It has been demonstrated that the β relaxation is largely responsible for the free-volume hole anisotropy after simple shear orientation. Upon the removal of mechanical force, the deformation of the free volume is mostly reversible at temperatures much lower than the glass transition. No strong correlation between macroscopic deformation and the free-volume hole deformation was found regardless of molecular orientation.
C60 molecular dynamics studied by muon spin relaxation
In muonium-substituted organic radicals, the muon spin can serve as a probe of molecular dynamics. The motional perturbation induces transitions between the coupled spin states of muon and unpaired electron. Studies of the resultant muon spin relaxation in C60Mu, the species formed by muon implantation in solid C60, yield the correlation time characteristic of the reorientational motion
The molecular basis of anesthesia studied by solvent relaxation technique
Barucha-Kraszewska, Justyna; Przybylo, M.; Langner, M.; Hof, Martin
Regensburg : Digital Print Group O. Schimek GmbH, 2007. s. 262-262. [Conference on Methods and Applications of Fluorescence /10./. 09.09.2007-12.09.2007, Salzburg] Institutional research plan: CEZ:AV0Z40400503 Keywords : solvent relaxation * molecular basis Subject RIV: CF - Physical ; Theoretical Chemistry
Rotational relaxation of molecular hydrogen at moderate temperatures
Sharma, S. P.
1994-01-01
Using a coupled rotation-vibration-dissociation model the rotational relaxation times for molecular hydrogen as a function of final temperature (500-5000 K), in a hypothetical scenario of sudden compression, are computed. The theoretical model is based on a master equation solver. The bound-bound and bound-free transition rates have been computed using a quasiclassical trajectory method. A review of the available experimental data on the rotational relaxation of hydrogen is presented, with a critical overview of the method of measurements and data reduction, including the sources of errors. These experimental data are then compared with the computed results.
Experimentally Constrained Molecular Relaxation: The case of hydrogenated amorphous silicon
Biswas, Parthapratim; Atta-Fynn, Raymond; Drabold, David A.
2007-01-01
We have extended our experimentally constrained molecular relaxation technique (P. Biswas {\\it et al}, Phys. Rev. B {\\bf 71} 54204 (2005)) to hydrogenated amorphous silicon: a 540-atom model with 7.4 % hydrogen and a 611-atom model with 22 % hydrogen were constructed. Starting from a random configuration, using physically relevant constraints, {\\it ab initio} interactions and the experimental static structure factor, we construct realistic models of hydrogenated amorphous silicon. Our models ...
Low-temperature magnetization relaxation in magnetic molecular solids
Vijayaraghavan, Avinash; Garg, Anupam, E-mail: agarg@northwestern.edu
2013-08-15
The low temperature relaxation of the magnetization in molecular magnetic solids such as Fe{sub 8} is studied using Monte Carlo simulations. A set of rate equations is then developed to understand the simulations, and the results are compared. The simulations show that the magnetization of an initially saturated sample deviates as a square-root in time at short times, as observed experimentally, and this law is derived from the rate equations analytically. -- Highlights: •A novel set of non-linear rate equations for the coupled evolution of the magnetization and dipole field distribution. •An analytic derivation of the short-time square root in time behavior of the magnetization relaxation. •Agreement between theory and simulations without further fitting parameters.
Polymer degradation and molecular relaxation during accelerated weathering of coatings
Fernando, B. Malcolm Dilhan
2011-12-01
A model polyester-urethane coating similar to those on USAF aircraft was the focus in this research. It was studied for physical property changes during accelerated weathering. Isothermal aging and natural weathering were utilized as control studies. Coatings subjected to accelerated weathering had an increase in tensile modulus, glass transition temperature and surface stiffness. DSC analysis of these coatings clearly showed evidence for 'physical aging'. This phenomenon was pursued further to find out the impact of macromolecular relaxation on the polymer physical properties. The unique feature of this research is the investigation of kinetics of macromolecular relaxation whilst a polymer undergoes simultaneous degradation. Assessment was done for some material parameters as found in theoretical models. Fictive temperature (Tf), apparent activation energy (Deltah*/R) and non linearity parameter ( x) found in Tool-Narayanswamy-Moyniham (TNM) model were explored. Tf was found to be decreasing with weathering and explained the increasingly aged 'state' of the structure. Deltah*/R was found to be increasing and explains an increased energy barrier to overcome to attain relaxation. DSC peak-shift method was used to characterize x. At early stages there is a stronger non linearity of relaxation (lower x) with a stronger structure dependence and later the relaxation kinetics seems more temperature dependent (higher x). MDSC was done to characterize the non exponentiality parameter (beta) as found in the Kohlrauch-Williams-Watts (KWW) equation. Decreasing beta value with exposure implies an increasingly broad distribution of relaxation times. The Cooperatively Rearranging Regions (CRR) concept of Adams and Gibbs was also examined. Molecular weight (Ma) of the volume (Va) represented by a CRR was compared with Mc, the molecular weight between crosslinks. Nanoindentation was done to explore the coatings' surface mechanical properties. During accelerated weathering the
Molecular alignment relaxation in polymer optical fibers for sensing applications
Stajanca, Pavol; Cetinkaya, Onur; Schukar, Marcus; Mergo, Pawel; Webb, David J.; Krebber, Katerina
2016-03-01
A systematic study of annealing behavior of drawn PMMA fibers was performed. Annealing dynamics were investigated under different environmental conditions by fiber longitudinal shrinkage monitoring. The shrinkage process was found to follow a stretched exponential decay function revealing the heterogeneous nature of the underlying molecular dynamics. The complex dependence of the fiber shrinkage on initial degree of molecular alignment in the fiber, annealing time and temperature was investigated and interpreted. Moreover, humidity was shown to have a profound effect on the annealing process, which was not recognized previously. Annealing was also shown to have considerable effect on the fiber mechanical properties associated with the relaxation of molecular alignment in the fiber. The consequences of fiber annealing for the climatic stability of certain polymer optical fiber-based sensors are discussed, emphasizing the importance of fiber controlled pre-annealing with respect to the foreseeable operating conditions.
Excitation Dynamics and Relaxation in a Molecular Heterodimer
Balevicius, V; Abramavicius, D; Mancal, T; Valkunas, L
2011-01-01
The exciton dynamics in a molecular heterodimer is studied as a function of differences in excitation and reorganization energies, asymmetry in transition dipole moments and excited state lifetimes. The heterodimer is composed of two molecules modeled as two-level systems coupled by the resonance interaction. The system-bath coupling is taken into account as a modulating factor of the energy gap of the molecular excitation, while the relaxation to the ground state is treated phenomenologically. Comparison of the description of the excitation dynamics modeled using either the Redfield equations (secular and full forms) or the Hierarchical quantum master equation (HQME) is demonstrated and discussed. Possible role of the dimer as an excitation quenching center in photosynthesis self-regulation is discussed. It is concluded that the system-bath interaction rather than the excitonic effect determines the excitation quenching ability of such a dimer.
Bayesian molecular phylogenetics: estimation of divergence dates and hypothesis testing
Aris-Brosou, S.
2002-01-01
With the advent of automated sequencing, sequence data are now available to help us understand the functioning of our genome, as well as its history. To date,powerful methods such as maximum likelihood have been used to estimate its mode and tempo of evolution and its branching pattern. However, these methods appear to have some limitations. The purpose of this thesis is to examine these issues in light of Bayesian modelling, taking advantage of some recent advances in Bayesian compu...
Fitz, Benjamin David
Segmental dynamics are investigated in model compounds, polymers, and network-forming polymers. Two aspects of these materials are investigated: (1) the role of molecular structure and connectivity on determining the characteristics of the segmental relaxation, and (2) monitoring the variations in the segmental dynamics during network-forming chemical reactions. We quantify the most important aspects of the dynamics: the relaxation shape, the relaxation strength, the relaxation time, and the temperature dependencies of these properties. Additionally, two general segmental dynamics issues of interest are the length-scale and the homogeneous/heterogeneous aspects. A judicious choice of network-forming polymer provides for the determination of an upper bound on the length-scale. A comparison of relaxation characteristics between dynamic light scattering (measuring density fluctuations) and dielectric relaxation spectroscopy (measuring segmental dipolar reorientation) provides one evaluation of the heterogeneity issue. Dipole dynamics in small molecule model compounds show the influence of molecular connectivity on the cooperative molecular response associated with the glass transition. A rigid, nonpolar, cyanate ester network is shown to develop an anomalous relaxation process during crosslinking. A specific local mode of motion is assigned. Additionally, the main relaxation becomes extraordinarily broad during the course of the network formation, due to markedly increased segmental rigidity and loss of configurational entropy.
Generalized extended Navier-Stokes theory: multiscale spin relaxation in molecular fluids.
Hansen, J S
2013-09-01
This paper studies the relaxation of the molecular spin angular velocity in the framework of generalized extended Navier-Stokes theory. Using molecular dynamics simulations, it is shown that for uncharged diatomic molecules the relaxation time decreases with increasing molecular moment of inertia per unit mass. In the regime of large moment of inertia the fast relaxation is wave-vector independent and dominated by the coupling between spin and the fluid streaming velocity, whereas for small inertia the relaxation is slow and spin diffusion plays a significant role. The fast wave-vector-independent relaxation is also observed for highly packed systems. The transverse and longitudinal spin modes have, to a good approximation, identical relaxation, indicating that the longitudinal and transverse spin viscosities have same value. The relaxation is also shown to be isomorphic invariant. Finally, the effect of the coupling in the zero frequency and wave-vector limit is quantified by a characteristic length scale; if the system dimension is comparable to this length the coupling must be included into the fluid dynamical description. It is found that the length scale is independent of moment of inertia but dependent on the state point. PMID:24125208
Molecular excitation dynamics and relaxation quantum theory and spectroscopy
Valkunas, Leonas; Mancal, Tomas
2013-01-01
Meeting the need for a work that brings together quantum theory and spectroscopy to convey excitation processes to advanced students and specialists wishing to conduct research and understand the entire field rather than just single aspects.Written by an experienced author and recognized authority in the field, this text covers numerous applications and offers examples taken from different disciplines. As a result, spectroscopists, molecular physicists, physical chemists, and biophysicists will all find this a must-have for their research. Also suitable as supplementary reading in graduate
A study of internal energy relaxation in shocks using molecular dynamics based models
Recent potential energy surfaces (PESs) for the N2 + N and N2 + N2 systems are used in molecular dynamics (MD) to simulate rates of vibrational and rotational relaxations for conditions that occur in hypersonic flows. For both chemical systems, it is found that the rotational relaxation number increases with the translational temperature and decreases as the rotational temperature approaches the translational temperature. The vibrational relaxation number is observed to decrease with translational temperature and approaches the rotational relaxation number in the high temperature region. The rotational and vibrational relaxation numbers are generally larger in the N2 + N2 system. MD-quasi-classical trajectory (QCT) with the PESs is also used to calculate the V-T transition cross sections, the collision cross section, and the dissociation cross section for each collision pair. Direct simulation Monte Carlo (DSMC) results for hypersonic flow over a blunt body with the total collision cross section from MD/QCT simulations, Larsen-Borgnakke with new relaxation numbers, and the N2 dissociation rate from MD/QCT show a profile with a decreased translational temperature and a rotational temperature close to vibrational temperature. The results demonstrate that many of the physical models employed in DSMC should be revised as fundamental potential energy surfaces suitable for high temperature conditions become available
A study of internal energy relaxation in shocks using molecular dynamics based models
Li, Zheng, E-mail: zul107@psu.edu; Parsons, Neal, E-mail: neal.parsons@cd-adapco.com [Department of Aerospace Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States); Levin, Deborah A., E-mail: deblevin@illinois.edu [Department of Aerospace Engineering, University of Illinois Urbana-Champaign, Urbana, Illinois 61801-2935 (United States)
2015-10-14
Recent potential energy surfaces (PESs) for the N{sub 2} + N and N{sub 2} + N{sub 2} systems are used in molecular dynamics (MD) to simulate rates of vibrational and rotational relaxations for conditions that occur in hypersonic flows. For both chemical systems, it is found that the rotational relaxation number increases with the translational temperature and decreases as the rotational temperature approaches the translational temperature. The vibrational relaxation number is observed to decrease with translational temperature and approaches the rotational relaxation number in the high temperature region. The rotational and vibrational relaxation numbers are generally larger in the N{sub 2} + N{sub 2} system. MD-quasi-classical trajectory (QCT) with the PESs is also used to calculate the V-T transition cross sections, the collision cross section, and the dissociation cross section for each collision pair. Direct simulation Monte Carlo (DSMC) results for hypersonic flow over a blunt body with the total collision cross section from MD/QCT simulations, Larsen-Borgnakke with new relaxation numbers, and the N{sub 2} dissociation rate from MD/QCT show a profile with a decreased translational temperature and a rotational temperature close to vibrational temperature. The results demonstrate that many of the physical models employed in DSMC should be revised as fundamental potential energy surfaces suitable for high temperature conditions become available.
Inhomogeneous Relaxation of a Molecular Layer on an Insulator due to Compressive Stress
Bocquet, F.; Nony, L.; Mannsfeld, S. C. B.; Oison, V.; Pawlak, R.; Porte, L.; Loppacher, Ch.
2012-05-01
We discuss the inhomogeneous stress relaxation of a monolayer of hexahydroxytriphenylene (HHTP) which adopts the rare line-on-line (LOL) coincidence on KCl(001) and forms moiré patterns. The fact that the hexagonal HHTP layer is uniaxially compressed along the LOL makes this system an ideal candidate to discuss the influence of inhomogeneous stress relaxation. Our work is a combination of noncontact atomic force microscopy experiments, density functional theory and potential energy calculations, and a thorough interpretation by means of the Frenkel-Kontorova model. We show that the assumption of a homogeneous molecular layer is not valid for this organic-inorganic heteroepitaxial system since the best calculated energy configuration correlates with the experimental data only if inhomogeneous relaxations of the layer are taken into account.
MOLECULAR DYNAMICS SIMULATION OF THE RELAXATION OF A FULLY EXTENDED POLYETHYLENE CHAIN
Yan Chen; Xiao-zhen Yang; Mao Xu; Ren-yuan Qian
1999-01-01
Molecular dynamics simulation of the relaxation at 300 K of a fully extended polyethylene chain of 800 CH2 units has been carried out by following the changes in morphology, van der Waals energy, radius of gyration in the sense of mechanics and gyration radius in the sense of Flory, population of trans-conformation and orientation factor. The relaxation went through three stages: (1) relaxation from the morphology of a straight rod of 100 nm length to the morphology close to a random coil of gyration radius 5.9nm in 110 ps; (2) collapse of the morphology of a coil to a highly compact globule close to a sphere of gyration radius 1.3 nm after 178 ps as the result of intersegmental van der Waals attractive interactions; (3)lateral ordering of the folded chain segments in the globule without appreciable changes in the chain dimension up to 1600 ps, the time limit of present simulation. Nearly complete relaxation of local segmental orientation was performed much faster than the relaxation of globule chain orientation even for a single chain of low degree of polymerization and at a temperature some 155℃ above its Tg. The lateral ordering of the chain segments during the period 178 to 680 ps of the simulation time was found to obey the Avrami equation with an Avrami index of 1.44.
The incoherent intermediate scattering function Sinc(Q,t) of polybutadiene (PB) and polyisobutylene (PIB) is measured on the neutron backscattering instrument IN16 in the ns-time range and in a temperature and pressure range where the observed relaxation is ascribed to segmental relaxation. Sinc(Q,t) at atmospheric pressure Patm, for PB at T=300 K and for PIB at T=368 K, shows a characteristic momentum transfer (Q) dependence, if fitted by a single stretched exponential relaxation process Sinc(Q,t)=A(Q)exp(-t/τKWW)β with fixed β=0.45 for PB and β=0.55 for PIB. For both polymers the Q-dependence of the relaxation time τKWW(Q) in the range 0.2 A-1-1 is compatible with a crossover from a power law τKWW(Q)∼Q-2/β at low Q to τKWW(Q)∼Q-2 at high Q. Application of pressure results for both polymers in an extension of the Q-2-range towards lower Q. A variation of the molecular weight (390w-2 behaviour. For Mwg we find relaxations at higher energy (0.1-1 meV) which we ascribe tentatively to end-of-chain motions. Furthermore, we show for PB the possibility to separate thermal and density effects onto Sinc(Q,t) by controlling pressure along different thermodynamic paths
Valentini, Paolo; Zhang, Chonglin; Schwartzentruber, Thomas E.
2012-10-01
We study the rotational relaxation process in nitrogen using all-atom molecular dynamics (MD) simulations and direct simulation Monte Carlo (DSMC). The intermolecular model used in the MD simulations is shown to (i) reproduce very well the shear viscosity of nitrogen over a wide range of temperatures, (ii) predict the near-equilibrium rotational collision number in good agreement with published trajectory calculations done on ab initio potential energy surfaces, and (iii) produce shock wave profiles in excellent accordance with the experimental measurements. We find that the rotational relaxation process is dependent not only on the near-equilibrium temperature (i.e., when systems relax to equilibrium after a small perturbation), but more importantly on both the magnitude and direction of the initial deviation from the equilibrium state. The comparison between MD and DSMC, based on the Borgnakke-Larsen model, for shock waves (both at low and high temperatures) and one-dimensional expansions shows that a judicious choice of a constant Zrot can produce DSMC results which are in relatively good agreement with MD. However, the selection of the rotational collision number is case-specific, depending not only on the temperature range, but more importantly on the type of flow (compression or expansion), with significant limitations for more complex simulations characterized both by expansion and compression zones. Parker's model, parametrized for nitrogen, overpredicts Zrot for temperatures above about 300 K. It is also unable to describe the dependence of the relaxation process on the direction to equilibrium. Finally, we present a demonstrative cell-based formulation of a rotational relaxation model to illustrate how, by including the key physics obtained from the MD data (dependence of the relaxation process on both the rotational and the translational state of the gas), the agreement between MD and DSMC solutions is drastically improved.
Holmes, R. J.; Forrest, S. R.
2005-06-01
We examine the influence of singlet-triplet intersystem crossing (ISC) and excited-state molecular relaxation on strong exciton-photon coupling in optical microcavities filled with small-molecular-weight organic materials. The effect of ISC is considered by comparing coupling effects in the phosphorescent organic platinum(II) octaethylporphyrin to those in the fluorescent free-base porphyrin tetraphenylporphyrin (TPP). The influence of excited-state molecular relaxation is studied by examining coupling to the Soret band of TPP. Both ISC and excited-state molecular relaxation prevent the population of polariton states under nonresonant optical excitation. The interplay between strong coupling and relaxation processes offers a unique opportunity to directly probe fundamental ultrafast excitonic phenomena. The competition between coupling in microcavities and these processes allows for estimation of their relative transition rates.
Multi spin systems with spin 1/2 nuclei and dipolar coupled quadrupolar nuclei can show so called ''quadrupolar dips''. There are two main reasons for this behavior: polarization transfer and relaxation. They look quite alike and without additional research cannot be differentiated easily in most cases. These two phenomena have quite different physical and theoretical backgrounds. For no or very slow dynamics, polarization transfer will take place, which is energy conserving inside the spin system. This effect can entirely be described using quantum mechanics on the spin system. Detailed knowledge about the crystallography is needed, because this affects the relevant hamiltonians directly. For systems with fast enough dynamics, relaxation takes over, and the energy flows from the spin system to the lattice; thus a more complex theoretical description is needed. This description has to include a dynamic model, usually in the form of a spectral density function. Both models should include detailed modelling of the complete spin system. A software library was developed to be able to model complex spin systems. It allows to simulate polarization transfer or relaxation effects. NMR measurements were performed on the protonic conductor K3H(SO4)2. A single crystal shows sharp quadrupolar dips at room temperature. Dynamics could be excluded using relaxation measurements and literature values. Thus, a polarization transfer analysis was used to describe those dips with good agreement. As a second system, imidazolium based molecular crystals were analyzed. The quadrupolar dips were expected to be caused by polarization transfer; this was carefully analyzed and found not to be true. A relaxation based analysis shows good agreement with the measured data in the high temperature area. It leverages a two step spectral density function, which indicates two distinct dynamic processes happening in this system.
Madhuchhanda Bhattacharjee
Full Text Available Both molecular marker and gene expression data were considered alone as well as jointly to serve as additive predictors for two pathogen-activity-phenotypes in real recombinant inbred lines of soybean. For unobserved phenotype prediction, we used a bayesian hierarchical regression modeling, where the number of possible predictors in the model was controlled by different selection strategies tested. Our initial findings were submitted for DREAM5 (the 5th Dialogue on Reverse Engineering Assessment and Methods challenge and were judged to be the best in sub-challenge B3 wherein both functional genomic and genetic data were used to predict the phenotypes. In this work we further improve upon this previous work by considering various predictor selection strategies and cross-validation was used to measure accuracy of in-data and out-data predictions. The results from various model choices indicate that for this data use of both data types (namely functional genomic and genetic simultaneously improves out-data prediction accuracy. Adequate goodness-of-fit can be easily achieved with more complex models for both phenotypes, since the number of potential predictors is large and the sample size is not small. We also further studied gene-set enrichment (for continuous phenotype in the biological process in question and chromosomal enrichment of the gene set. The methodological contribution of this paper is in exploration of variable selection techniques to alleviate the problem of over-fitting. Different strategies based on the nature of covariates were explored and all methods were implemented under the bayesian hierarchical modeling framework with indicator-based covariate selection. All the models based in careful variable selection procedure were found to produce significant results based on permutation test.
Roed, Lisa Anita; Niss, Kristine; Jakobsen, Bo
2015-01-01
liquids in which different physical relaxation processes are both as function of temperature and pressure/density governed by the same underlying “inner clock.” Furthermore, the results are discussed in terms of the recent conjecture that van der Waals liquids, like the measuredliquid, comply to the......The frequency dependent specific heat has been measured under pressure for the molecular glass forming liquid 5-polyphenyl-4-ether in the viscous regime close to the glass transition. The temperature and pressure dependences of the characteristic time scale associated with the specific heat is...
Dielectric relaxation in ionic liquid/dipolar solvent binary mixtures: A semi-molecular theory
Daschakraborty, Snehasis; Biswas, Ranjit
2016-03-01
A semi-molecular theory is developed here for studying dielectric relaxation (DR) in binary mixtures of ionic liquids (ILs) with common dipolar solvents. Effects of ion translation on DR time scale, and those of ion rotation on conductivity relaxation time scale are explored. Two different models for the theoretical calculations have been considered: (i) separate medium approach, where molecularities of both the IL and dipolar solvent molecules are retained, and (ii) effective medium approach, where the added dipolar solvent molecules are assumed to combine with the dipolar ions of the IL, producing a fictitious effective medium characterized via effective dipole moment, density, and diameter. Semi-molecular expressions for the diffusive DR times have been derived which incorporates the effects of wavenumber dependent orientational static correlations, ion dynamic structure factors, and ion translation. Subsequently, the theory has been applied to the binary mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) with water (H2O), and acetonitrile (CH3CN) for which experimental DR data are available. On comparison, predicted DR time scales show close agreement with the measured DR times at low IL mole fractions (xIL). At higher IL concentrations (xIL > 0.05), the theory over-estimates the relaxation times and increasingly deviates from the measurements with xIL, deviation being the maximum for the neat IL by almost two orders of magnitude. The theory predicts negligible contributions to this deviation from the xIL dependent collective orientational static correlations. The drastic difference between DR time scales for IL/solvent mixtures from theory and experiments arises primarily due to the use of the actual molecular volume ( Vmol dip ) for the rotating dipolar moiety in the present theory and suggests that only a fraction of Vmol dip is involved at high xIL. Expectedly, nice agreement between theory and experiments appears when experimental
Conversion of an atomic to a molecular argon ion and low pressure argon relaxation
M, N. Stankov; A, P. Jovanović; V, Lj Marković; S, N. Stamenković
2016-01-01
The dominant process in relaxation of DC glow discharge between two plane parallel electrodes in argon at pressure 200 Pa is analyzed by measuring the breakdown time delay and by analytical and numerical models. By using the approximate analytical model it is found that the relaxation in a range from 20 to 60 ms in afterglow is dominated by ions, produced by atomic-to-molecular conversion of Ar+ ions in the first several milliseconds after the cessation of the discharge. This conversion is confirmed by the presence of double-Gaussian distribution for the formative time delay, as well as conversion maxima in a set of memory curves measured in different conditions. Finally, the numerical one-dimensional (1D) model for determining the number densities of dominant particles in stationary DC glow discharge and two-dimensional (2D) model for the relaxation are used to confirm the previous assumptions and to determine the corresponding collision and transport coefficients of dominant species and processes. Project supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia (Grant No. ON171025).
Simple molecular mechanism of heat transfer: Debye relaxation versus power-law
We study a simple molecular model (at coarse-grain level) as a basis of irreversible heat transfer through a diathermic partition. The partition separates into two adjacent parts a box containing ideal point particles that communicate only though this partition. We provide the basic mechanism of energy transfer between the left- and right-hand side gas samples by assuming equipartition of kinetic energy of all outgoing particles colliding with the partition at a given time. We analyse and compare two essentially different cases (A) the reference one, where we assume that the border walls of the box and the diathermic partitions can randomize the direction of motion of rebounding particles, and (B) the case where we assume the mirror collisions of particles with the border walls and the partition. In both cases the rebounding of the particles from border walls is elastic. The above introduced assumptions allow us to numerically simulate and analytically consider, for example, the relaxation of temperatures of both gas samples and the entropy of the system. However, in both cases the long-time relaxation is essentially different since in case (A) it is an exponential one, while in case (B) it seems to be a power-law relaxation. The obtained results well agree in case (A) with the predictions of the phenomenological, linear theory of irreversible theory had to be developed which assumes time-dependence of heat conductivity; it describes the relaxation of the system far from equilibrium. The explanation of the results obtained in this case is, nevertheless, an intriguing problem. (author)
Water interactions with varying molecular states of bovine casein: 2H NMR relaxation studies
The caseins occur in milk as spherical colloidal complexes of protein and salts with an average diameter of 1200 A, the casein micelles. Removal of Ca2+ is thought to result in their dissociation into smaller protein complexes stabilized by hydrophobic interactions and called submicelles. Whether these submicelles actually occur within the micelles as discrete particles interconnected by calcium phosphate salt bridges has been the subject of much controversy. A variety of physical measurements have shown that casein micelles contain an inordinately high amount of trapped water (2 to 7 g H2O/g protein). With this in mind it was of interest to determine if NMR relaxation measurements could detect the presence of this trapped water within the micelles, and to evaluate whether it is a continuum with picosecond correlation times or is associated in part with discrete submicellar structures with nanosecond motions. For this purpose the variations in 2H NMR longitudinal and transverse relaxation rates of water with protein concentration were determined for bovine casein at various temperatures, under both submicellar and micellar conditions. D2O was used instead of H2O to eliminate cross-relaxation effects. From the protein concentration dependence of the relaxation rates, the second virial coefficient of the protein was obtained by nonlinear regression analysis. Using either an isotropic tumbling or an intermediate asymmetry model, degrees of hydration, v, and correlation times, tau c, were calculated for the caseins; from the latter parameter the Stokes radius, r, was obtained. Next, estimates of molecular weights were obtained from r and the partial specific volume. Values were in the range of those published from other methodologies for the submicelles
Inhibited, Explosive and Anisotropic Relaxation in a Gas of Molecular Super-Rotors
Khodorkovsky, Yuri; Hartmann, Jean-Michel; Averbukh, Ilya Sh
2015-01-01
Recently, several femtosecond laser techniques have been developed that are capable of bringing gas molecules to extremely fast rotation in a very short time, while keeping their translational motion intact and relatively slow. We investigate collisional equilibration dynamics of this new state of molecular gases, and find that it follows a remarkable generic scenario. The route to equilibrium starts with a durable metastable 'gyroscopic stage', in the course of which the molecules maintain their fast rotation and orientation of the angular momentum through many collisions. The inhibited rotational-translational relaxation is characterized by a persistent anisotropy in the molecular angular distribution, and is manifested in the long-lasting optical birefringence, and anisotropic diffusion in the gas. After a certain induction time, the 'gyroscopic stage' is abruptly terminated by a self-accelerating explosive rotational-translational energy exchange leading the gas towards the final thermal equilibrium. We i...
J Colmenero; A Arbe; F Alvarez; A Narros; D Richter; M Monkenbush; B Farago
2004-07-01
The combination of molecular dynamics simulations and neutron scattering measurements on three different glass-forming polymers (polyisoprene, poly(vinyl ethylene) and polybutadiene) has allowed to establish the existence of a crossover from Gaussian to non-Gaussian behavior for the incoherent scattering function in the -relaxation regime. The deviation from Gaussian behavior observed can be reproduced assuming the existence of a distribution of discrete jump lengths underlying the sublinear diffusion of the atomic motions during the structural relaxation.
Tacke, Christian
2015-07-01
Multi spin systems with spin 1/2 nuclei and dipolar coupled quadrupolar nuclei can show so called ''quadrupolar dips''. There are two main reasons for this behavior: polarization transfer and relaxation. They look quite alike and without additional research cannot be differentiated easily in most cases. These two phenomena have quite different physical and theoretical backgrounds. For no or very slow dynamics, polarization transfer will take place, which is energy conserving inside the spin system. This effect can entirely be described using quantum mechanics on the spin system. Detailed knowledge about the crystallography is needed, because this affects the relevant hamiltonians directly. For systems with fast enough dynamics, relaxation takes over, and the energy flows from the spin system to the lattice; thus a more complex theoretical description is needed. This description has to include a dynamic model, usually in the form of a spectral density function. Both models should include detailed modelling of the complete spin system. A software library was developed to be able to model complex spin systems. It allows to simulate polarization transfer or relaxation effects. NMR measurements were performed on the protonic conductor K{sub 3}H(SO{sub 4}){sub 2}. A single crystal shows sharp quadrupolar dips at room temperature. Dynamics could be excluded using relaxation measurements and literature values. Thus, a polarization transfer analysis was used to describe those dips with good agreement. As a second system, imidazolium based molecular crystals were analyzed. The quadrupolar dips were expected to be caused by polarization transfer; this was carefully analyzed and found not to be true. A relaxation based analysis shows good agreement with the measured data in the high temperature area. It leverages a two step spectral density function, which indicates two distinct dynamic processes happening in this system.
Molecular-dynamics study of amorphous SiO{sub 2} relaxation
Fadhilah, Irfan Muhammad, E-mail: irfanmuhammadf@ymail.com [Department of Physics, Universitas Padjadjaran, Jatinangor, Sumedang 45363 (Indonesia); Rosandi, Yudi, E-mail: rosandi@geophys.unpad.ac.id [Theoretical and Computational Geophysics Laboratory, Department of Physics, Universitas Padjadjaran, Jatinangor, Sumedang 45363 (Indonesia)
2015-09-30
Using Molecular-Dynamics simulation we observed the generation of amorphous SiO{sub 2} target from a randomly distributed Si and O atoms. We applied a sequence of annealing of the target with various temperature and quenching to room temperature. The relaxation time required by the system to form SiO{sub 4} tetrahedral mesh after a relatively long simulation time, is studied. The final amorphous target was analyzed using the radial distribution function method, which can be compared with the available theoretical and experimental data. We found that up to 70% of the target atoms form the tetrahedral SiO{sub 4} molecules. The number of formed tetrahedral increases following the growth function and the rate of SiO{sub 4} formation follows Arrhenius law, depends on the annealing temperature. The local structure of amorphous SiO{sub 2} after this treatment agrees well with those reported in some literatures.
Dielectric relaxation spectra of liquid crystals in relation to molecular structure
The dielectric spectra obtained for some members of two homologous series, i.e. for di-alkoxyazoxybenzenes and penthyl-alkoxythiobenzoates, are discussed qualitatively on the basis of the Nordio-Rigatti-Segre diffusion model. It is additionally assumed that the molecular reorientations take place about the principal axes of the inertia tensor. The distribution of correlation times, which is strongly temperature dependent in the vicinity of the clearing point, is interpreted as being caused by fluctuations of the principal axes frame which are due to conformation changes inside the end chains. The Bauer equation is used to describe both principal molecular reorientations, i.e. the reorientations about the long and short axis, observed in liquid crystalline structure by means of dielectric relaxation methods. The energies and entropies of activation have been computed for both principal reorientations. The differences between the high frequency limit of the dielectric permittivity and the refractive index squared of liquid crystals are explained in terms of two librational motions of the molecules observed by other experimental techniques, viz. far infra-red, Raman and inelastic neutron scattering spectroscopies, and found in this work on the basis of dielectrically measured energy barriers. It has been shown qualitatively that intramolecular libratory motions greatly effect the high frequency dielectric spectrum. Finally, molecular motions in liquid crystals are divided into two types: coherent and incoherent. 127 refs., 56 figs., 17 tabs. (author)
A C Ribeiro; P J Sebastiao; C Cruz
2003-08-01
We present in this work a review concerning wide frequency range 1 proton NMR relaxation studies performed in compounds exhibiting columnar mesophases, namely the Colho mesophase in the case of a liquid crystal of discotic molecules and the h mesophase in the case of a liquid crystal of biforked molecules. These NMR relaxation studies were performed combining conventional and fast ﬁeld cycling NMR techniques in a frequency range between 100 Hz and 300 MHz. The possibility of probing such a large frequency range has provided a way to effectively distinguish the inﬂuence, on the 1 relaxation proﬁles, of the different molecular movements observed in this type of mesophases. In addition, we present a comparison between the molecular dynamics in columnar (h) and lamellar (SmC) mesophases exhibited by the same biforked compound.
Bayesian ensemble refinement by replica simulations and reweighting
Hummer, Gerhard; Köfinger, Jürgen
2015-12-01
We describe different Bayesian ensemble refinement methods, examine their interrelation, and discuss their practical application. With ensemble refinement, the properties of dynamic and partially disordered (bio)molecular structures can be characterized by integrating a wide range of experimental data, including measurements of ensemble-averaged observables. We start from a Bayesian formulation in which the posterior is a functional that ranks different configuration space distributions. By maximizing this posterior, we derive an optimal Bayesian ensemble distribution. For discrete configurations, this optimal distribution is identical to that obtained by the maximum entropy "ensemble refinement of SAXS" (EROS) formulation. Bayesian replica ensemble refinement enhances the sampling of relevant configurations by imposing restraints on averages of observables in coupled replica molecular dynamics simulations. We show that the strength of the restraints should scale linearly with the number of replicas to ensure convergence to the optimal Bayesian result in the limit of infinitely many replicas. In the "Bayesian inference of ensembles" method, we combine the replica and EROS approaches to accelerate the convergence. An adaptive algorithm can be used to sample directly from the optimal ensemble, without replicas. We discuss the incorporation of single-molecule measurements and dynamic observables such as relaxation parameters. The theoretical analysis of different Bayesian ensemble refinement approaches provides a basis for practical applications and a starting point for further investigations.
Nuclear magnetic relaxation, correlation time spectrum, and molecular dynamics in a linear polymer
The pulsed nuclear magnetic resonance (NMR) method at a proton frequency of 25 MHz at temperatures of 22-160oC is used to detect the transverse magnetization decay in polyisoprene rubbers with various molecular masses, to determine the NMR damping time T2, and to measure spin-lattice relaxation time T1 and time T2eff of damping of solid-echo signals under the action of a sequence of MW-4 pulses modified by introducing 180o pulses. The dispersion dependences of T2eff obtained for each temperature are combined into one using the temperature-frequency equivalence principle. On the basis of the combined dispersion dependence of T2eff and the data on T2 and T1, the correlation time spectrum of molecular movements is constructed. Analysis of the shape of this spectrum shows that the dynamics of polymer molecules can be described in the first approximation by the Doi-Edwards tube-reptation model
Almond, A; Bunkenborg, Jakob; Franch, T; Gotfredsen, Charlotte Held; Duus, J O
2001-01-01
An investigation has been performed to assess how aqueous dynamical simulations of flexible molecules can be compared against NMR data. The methodology compares state-of-the-art NMR data (residual dipolar coupling, NOESY, and (13)C relaxation) to molecular dynamics simulations in water over sever...
Xie, Wen Jun; Yang, Yi Isaac; Gao, Yi Qin, E-mail: gaoyq@pku.edu.cn [Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering and Biodynamic Optical Imaging Center, Peking University, Beijing 100871 (China)
2015-12-14
In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics.
In this study, we examine how complex ions such as oxyanions influence the dynamic properties of water and whether differences exist between simple halide anions and oxyanions. Nitrate anion is taken as an example to investigate the hydration properties of oxyanions. Reorientation relaxation of its hydration water can occur through two different routes: water can either break its hydrogen bond with the nitrate to form one with another water or switch between two oxygen atoms of the same nitrate. The latter molecular mechanism increases the residence time of oxyanion’s hydration water and thus nitrate anion slows down the translational motion of neighbouring water. But it is also a “structure breaker” in that it accelerates the reorientation relaxation of hydration water. Such a result illustrates that differences do exist between the hydration of oxyanions and simple halide anions as a result of different molecular geometries. Furthermore, the rotation of the nitrate solute is coupled with the hydrogen bond rearrangement of its hydration water. The nitrate anion can either tilt along the axis perpendicularly to the plane or rotate in the plane. We find that the two reorientation relaxation routes of the hydration water lead to different relaxation dynamics in each of the two above movements of the nitrate solute. The current study suggests that molecular geometry could play an important role in solute hydration and dynamics
Relaxed Molecular Clock Provides Evidence for Long-Distance Dispersal of Nothofagus (Southern Beech
Knapp Michael
2005-01-01
Full Text Available Nothofagus (southern beech, with an 80-million-year-old fossil record, has become iconic as a plant genus whose ancient Gondwanan relationships reach back into the Cretaceous era. Closely associated with Wegener's theory of "Kontinentaldrift", Nothofagus has been regarded as the "key genus in plant biogeography". This paradigm has the New Zealand species as passengers on a Moa's Ark that rafted away from other landmasses following the breakup of Gondwana. An alternative explanation for the current transoceanic distribution of species seems almost inconceivable given that Nothofagus seeds are generally thought to be poorly suited for dispersal across large distances or oceans. Here we test the Moa's Ark hypothesis using relaxed molecular clock methods in the analysis of a 7.2-kb fragment of the chloroplast genome. Our analyses provide the first unequivocal molecular clock evidence that, whilst some Nothofagus transoceanic distributions are consistent with vicariance, trans-Tasman Sea distributions can only be explained by long-distance dispersal. Thus, our analyses support the interpretation of an absence of Lophozonia and Fuscospora pollen types in the New Zealand Cretaceous fossil record as evidence for Tertiary dispersals of Nothofagus to New Zealand. Our findings contradict those from recent cladistic analyses of biogeographic data that have concluded transoceanic Nothofagus distributions can only be explained by vicariance events and subsequent extinction. They indicate that the biogeographic history of Nothofagus is more complex than envisaged under opposing polarised views expressed in the ongoing controversy over the relevance of dispersal and vicariance for explaining plant biodiversity. They provide motivation and justification for developing more complex hypotheses that seek to explain the origins of Southern Hemisphere biota.
Relaxed molecular clock provides evidence for long-distance dispersal of Nothofagus (southern beech.
Michael Knapp
2005-01-01
Full Text Available Nothofagus (southern beech, with an 80-million-year-old fossil record, has become iconic as a plant genus whose ancient Gondwanan relationships reach back into the Cretaceous era. Closely associated with Wegener's theory of "Kontinentaldrift", Nothofagus has been regarded as the "key genus in plant biogeography". This paradigm has the New Zealand species as passengers on a Moa's Ark that rafted away from other landmasses following the breakup of Gondwana. An alternative explanation for the current transoceanic distribution of species seems almost inconceivable given that Nothofagus seeds are generally thought to be poorly suited for dispersal across large distances or oceans. Here we test the Moa's Ark hypothesis using relaxed molecular clock methods in the analysis of a 7.2-kb fragment of the chloroplast genome. Our analyses provide the first unequivocal molecular clock evidence that, whilst some Nothofagus transoceanic distributions are consistent with vicariance, trans-Tasman Sea distributions can only be explained by long-distance dispersal. Thus, our analyses support the interpretation of an absence of Lophozonia and Fuscospora pollen types in the New Zealand Cretaceous fossil record as evidence for Tertiary dispersals of Nothofagus to New Zealand. Our findings contradict those from recent cladistic analyses of biogeographic data that have concluded transoceanic Nothofagus distributions can only be explained by vicariance events and subsequent extinction. They indicate that the biogeographic history of Nothofagus is more complex than envisaged under opposing polarised views expressed in the ongoing controversy over the relevance of dispersal and vicariance for explaining plant biodiversity. They provide motivation and justification for developing more complex hypotheses that seek to explain the origins of Southern Hemisphere biota.
Critical thickness and strain relaxation in molecular beam epitaxy-grown SrTiO3 films
Wang, Tianqi; Ganguly, Koustav; Marshall, Patrick; Xu, Peng; Jalan, Bharat
2013-11-01
We report on the study of the critical thickness and the strain relaxation in epitaxial SrTiO3 film grown on (La0.3Sr0.7)(Al0.65Ta0.35)O3 (001) (LSAT) substrate using the hybrid molecular beam epitaxy approach. No change in the film's lattice parameter (both the in-plane and the out-of-plane) was observed up to a film thickness of 180 nm, which is in sharp contrast to the theoretical critical thickness of ˜12 nm calculated using the equilibrium theory of strain relaxation. For film thicknesses greater than 180 nm, the out-of-plane lattice parameter was found to decrease hyperbolically in an excellent agreement with the relaxation via forming misfit dislocations. Possible mechanisms are discussed by which the elastic strain energy can be accommodated prior to forming misfit dislocations leading to such anomalously large critical thickness.
Nuclear Spin Relaxation and Molecular Interactions of a Novel Triazolium-Based Ionic Liquid
Allen, Jesse J; Schneider, Yanika; Kail, Brian W; Luebke, David R; Nulwala, Hunaid; Damodaran, Krishnan
2013-04-11
Nuclear spin relaxation, small-angle X-ray scattering (SAXS), and electrospray ionization mass spectrometry (ESI-MS) techniques are used to determine supramolecular arrangement of 3-methyl-1-octyl-4-phenyl-1H-triazol-1,2,3-ium bis(trifluoromethanesulfonyl)imide [OMPhTz][Tf{sub 2}N], an example of a triazolium-based ionic liquid. The results obtained showed first-order thermodynamic dependence for nuclear spin relaxation of the anion. First-order relaxation dependence is interpreted as through-bond dipolar relaxation. Greater than first-order dependence was found in the aliphatic protons, aromatic carbons (including nearest neighbors), and carbons at the end of the aliphatic tail. Greater than first order thermodynamic dependence of spin relaxation rates is interpreted as relaxation resulting from at least one mechanism additional to through-bond dipolar relaxation. In rigid portions of the cation, an additional spin relaxation mechanism is attributed to anisotropic effects, while greater than first order thermodynamic dependence of the octyl side chain’s spin relaxation rates is attributed to cation–cation interactions. Little interaction between the anion and the cation was observed by spin relaxation studies or by ESI-MS. No extended supramolecular structure was observed in this study, which was further supported by MS and SAXS. nuclear Overhauser enhancement (NOE) factors are used in conjunction with spin–lattice relaxation time (T{sub 1}) measurements to calculate rotational correlation times for C–H bonds (the time it takes for the vector represented by the bond between the two atoms to rotate by one radian). The rotational correlation times are used to represent segmental reorientation dynamics of the cation. A combination of techniques is used to determine the segmental interactions and dynamics of this example of a triazolium-based ionic liquid.
Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of 15N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S2) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S2) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S2 values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S2 parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S2 calculated from the experimental NMR relaxation measurements, in a site-specific manner. - Highlights: • Correlation analysis between NMR relaxation measurements and MD simulations. • General order parameter (S2) as common reference between the two methods. • Different protein dynamics with different Histidine charge states in neutral pH. • Different protein dynamics with different water models
Liu, Qing; Shi, Chaowei [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Yu, Lu [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China); Zhang, Longhua [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Xiong, Ying, E-mail: yxiong73@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Tian, Changlin, E-mail: cltian@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China)
2015-02-13
Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of {sup 15}N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S{sup 2}) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S{sup 2}) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S{sup 2} values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S{sup 2} parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S{sup 2} calculated from the experimental NMR relaxation measurements, in a site-specific manner. - Highlights: • Correlation analysis between NMR relaxation measurements and MD simulations. • General order parameter (S{sup 2}) as common reference between the two methods. • Different protein dynamics with different Histidine charge states in neutral pH. • Different protein dynamics with different water models.
Influence of hydroxypropyl cellulose on molecular relaxations of epoxy-amine networks
Maria Inez G. Miranda; Dimitrios Samios; Liane de L. Freitas; Clara I. D. Bica
2013-01-01
A dynamic mechanical analysis (DMTA) study was conducted on epoxy-amine networks crosslinked in the presence of low contents of hydroxypropyl cellulose (HPC). The epoxy resin chosen was diglycidylether of bisphenol-A (DGEBA) and the crosslinker was 4,4'-diaminodiphenylmethane (DDM). In the glassy region, primary (α) and secondary (β, γ) relaxations originating from the epoxy and HPC components were well detected. Two primary relaxations of neat epoxy and epoxy/HPC systems, refe...
Inhomogeneous relaxation of a molecular layer on an insulator due to compressive stress
Bocquet, Franck; Nony, Laurent; Mannsfeld, Stefan; Oison, Vincent; Pawlak, Rémy; Porte, Louis; Loppacher, Christian
2012-01-01
We discuss the inhomogeneous stress relaxation of a monolayer of hexahydroxytriphenylene (HHTP) which adopts the rare line-on-line (lol) coincidence on KCl(001) and forms Moiré patterns. The fact that the hexagonal HHTP layer is uniaxially compressed along the lol makes this system an ideal candidate to discuss the influence of inhomogeneous stress relaxation. Our work is a combination of noncontact atomic force microscopy experiments, of density functional theory and potential energy calcula...
Influence of hydroxypropyl cellulose on molecular relaxations of epoxy-amine networks
Maria Inez G. Miranda
2013-01-01
Full Text Available A dynamic mechanical analysis (DMTA study was conducted on epoxy-amine networks crosslinked in the presence of low contents of hydroxypropyl cellulose (HPC. The epoxy resin chosen was diglycidylether of bisphenol-A (DGEBA and the crosslinker was 4,4'-diaminodiphenylmethane (DDM. In the glassy region, primary (α and secondary (β, γ relaxations originating from the epoxy and HPC components were well detected. Two primary relaxations of neat epoxy and epoxy/HPC systems, referred to as αepoxy and α'epoxy, could be detected, showing a particular glassy behavior for the systems studied in comparison with systems cured in bulk. The main relaxation temperature Tα (at the peak of αepoxy relaxation of the epoxy systems increased slightly with the addition of HPC. The activation energy for this transition (Tα of the epoxy-amine networks was determined both from tan δ and the peak temperatures for the loss modulus measured at various frequencies. The activation energy of the αepoxy relaxation determined from the loss modulus was more reliable than that based on tan δ. The addition of HPC lowered the activation energy of this αepoxy relaxation.
Shete, Ganesh; Khomane, Kailas S; Bansal, Arvind Kumar
2014-01-01
The purpose of this paper was to investigate the relaxation behavior of amorphous hesperetin (HRN), using dielectric spectroscopy, and assessment of its crystallization kinetics above glass transition temperature (Tg ). Amorphous HRN exhibited both local (β-) and global (α-) relaxations. β-Relaxation was observed below Tg , whereas α-relaxation prominently emerged above Tg . β-Relaxation was found to be of Johari-Goldstein type and was correlated with α-process by coupling model. Secondly, isothermal crystallization experiments were performed at 363 K (Tg + 16.5 K), 373 K (Tg + 26.5 K), and 383 K (Tg + 36.5 K). The kinetics of crystallization, obtained from the normalized dielectric strength, was modeled using the Avrami model. Havriliak-Negami (HN) shape parameters, αHN and αHN .βHN , were analyzed during the course of crystallization to understand the dynamics of amorphous phase during the emergence of crystallites. HN shape parameters indicated that long range (α-like) were motions affected to a greater extent than short range (β-like) motions during isothermal crystallization studies at all temperature conditions. The variable behavior of α-like motions at different isothermal crystallization temperatures was attributed to evolving crystallites with time and increase in electrical conductivity with temperature. PMID:24186540
Generalized extended Navier-Stokes theory: Multiscale spin relaxation in molecular fluids
Hansen, Jesper Schmidt
2013-01-01
per unit mass. In the regime of large moment of inertia the fast relaxation is wave-vector independent and dominated by the coupling between spin and the fluid streaming velocity, whereas for small inertia the relaxation is slow and spin diffusion plays a significant role. The fast wave-vector...... of the coupling in the zero frequency and wave-vector limit is quantified by a characteristic length scale; if the system dimension is comparable to this length the coupling must be included into the fluid dynamical description. It is found that the length scale is independent of moment of inertia but dependent...
Rotational relaxation in molecular hydrogen and deuterium: Theory versus acoustic experiments
Montero, S., E-mail: emsalvador@iem.cfmac.csic.es [Laboratory of Molecular Fluid Dynamics @ Instituto de Estructura de la Materia, CSIC, Serrano 121, 28006 Madrid (Spain); Pérez-Ríos, J. [Physics Department, Purdue University, West Lafayette, Indiana 47907 (United States)
2014-09-21
An explicit formulation of the rotational relaxation time in terms of state-to-state rate coefficients associated to inelastic collisions is reported. The state-to-state rates needed for the detailed interpretation of relaxation in H{sub 2} and D{sub 2}, including isotopic variant mixtures, have been calculated by solving the close-coupling Schrödinger equations using the H{sub 2}–H{sub 2} potential energy surface by Diep and Johnson [J. Chem. Phys. 112, 4465 (2000)]. Relaxation related quantities (rotational effective cross section, bulk viscosity, relaxation time, and collision number) calculated from first principles agree reasonably well with acoustic absorption experimental data on H{sub 2} and D{sub 2} between 30 and 293 K. This result confirms at once the proposed formulation, and the validation of the H{sub 2}–H{sub 2} potential energy surface employed, since no approximations have been introduced in the dynamics. Accordingly, the state-to-state rates derived from Diep and Johnson potential energy surface appear to be overestimated by up to 10% for H{sub 2}, and up to 30% for D{sub 2} at T = 300 K, showing a better agreement at lower temperatures.
Rotational relaxation in molecular hydrogen and deuterium: Theory versus acoustic experiments
An explicit formulation of the rotational relaxation time in terms of state-to-state rate coefficients associated to inelastic collisions is reported. The state-to-state rates needed for the detailed interpretation of relaxation in H2 and D2, including isotopic variant mixtures, have been calculated by solving the close-coupling Schrödinger equations using the H2–H2 potential energy surface by Diep and Johnson [J. Chem. Phys. 112, 4465 (2000)]. Relaxation related quantities (rotational effective cross section, bulk viscosity, relaxation time, and collision number) calculated from first principles agree reasonably well with acoustic absorption experimental data on H2 and D2 between 30 and 293 K. This result confirms at once the proposed formulation, and the validation of the H2–H2 potential energy surface employed, since no approximations have been introduced in the dynamics. Accordingly, the state-to-state rates derived from Diep and Johnson potential energy surface appear to be overestimated by up to 10% for H2, and up to 30% for D2 at T = 300 K, showing a better agreement at lower temperatures
Gill, Michelle L.; Palmer, Arthur G.
2014-01-01
The present work demonstrates that NMR spin relaxation rate constants for molecules interconverting between states with different diffusion tensors can be modeled theoretically by combining orientational correlation functions for exchanging spherical molecules with locally isotropic approximations for the diffusion anisotropic tensors. The resulting expressions are validated by comparison with correlation functions obtained by Monte Carlo simulations and are accurate for moderate degrees of d...
Faux, David A.; McDonald, Peter J.
2016-01-01
A model linking the molecular-scale dynamics of fluids confined to nano-pores to nuclear magnetic resonance (NMR) relaxation rates is proposed. The model is fit to experimental NMR dispersions for water and oil in an oil shale assuming that each fluid is characterised by three time constants and L\\'{e}vy statistics. Results yield meaningful and consistent intra-pore dynamical time constants, insight into diffusion mechanisms and pore morphology. The model is applicable to a wide range of poro...
Critical thickness and strain relaxation in molecular beam epitaxy-grown SrTiO{sub 3} films
Wang, Tianqi; Ganguly, Koustav; Marshall, Patrick; Xu, Peng; Jalan, Bharat [Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455 (United States)
2013-11-18
We report on the study of the critical thickness and the strain relaxation in epitaxial SrTiO{sub 3} film grown on (La{sub 0.3}Sr{sub 0.7})(Al{sub 0.65}Ta{sub 0.35})O{sub 3} (001) (LSAT) substrate using the hybrid molecular beam epitaxy approach. No change in the film's lattice parameter (both the in-plane and the out-of-plane) was observed up to a film thickness of 180 nm, which is in sharp contrast to the theoretical critical thickness of ∼12 nm calculated using the equilibrium theory of strain relaxation. For film thicknesses greater than 180 nm, the out-of-plane lattice parameter was found to decrease hyperbolically in an excellent agreement with the relaxation via forming misfit dislocations. Possible mechanisms are discussed by which the elastic strain energy can be accommodated prior to forming misfit dislocations leading to such anomalously large critical thickness.
Nonlinear relaxation dynamics in elastic networks and design principles of molecular machines
Togashi, Y.; A. Mikhailov
2007-01-01
Analyzing nonlinear conformational relaxation dynamics in elastic networks corresponding to two classical motor proteins, we find that they respond by well defined internal mechanical motions to various initial deformations and that these motions are robust against external perturbations. We show that this behavior is not characteristic for random elastic networks. However, special network architectures with such properties can be designed by evolutionary optimization methods. Using them, an ...
Huestis, D. L.
2008-12-01
Laboratory sound absorption measurements provide much of what we know about the vibrational kinetics of air mixtures, forming the core basis for retrieving the altitude profile of water in the mesosphere from infrared emissions between 6.3 and 6.9 μm. Here we show that sound-absorption and laser-excitation experiments follow exactly the same kinetics, reflect the same underlying reaction rates, and can be vulnerable to similar ambiguities. This has not been obvious because the literature lacks a consistent prescription for calculating the sound absorption frequency spectrum from the reaction rate coefficients. We have developed the first general theoretical formalism for calculating the absolute magnitude of sound absorption per-unit-length, versus sound frequency, for any number of collisional excitation, relaxation, and energy transfer processes, for any mixture of atomic and molecular gases. This new formalism, and the computer code that implements it, provide the first systematic means for inferring collisional rate coefficients from sound absorption measurements in which more than one rotational or vibrational mode is active, such as N2/O2/H2O/CO2 gas mixtures in the laboratory and the atmosphere. When a sound wave travels through a gas, the alternating compression and expansion cycles heat and cool the gas. If the acoustic frequency roughly matches the rate of vibrational relaxation, then the effective vibrational temperature lags behind the translational temperature and the energy in the sound wave is attenuated. The measured frequency of maximum absorption is proportional to the vibrational relaxation rate. In the simplest laser-based experiment, we excite a single molecular level and record its exponential time decay, with the vibrational relaxation rate being proportional to the decay frequency. In both experiments we derive the relaxation rate coefficient from the linear graph versus gas pressure. The technical problem is that any mixture of molecular
Gill, Michelle L; Palmer, Arthur G
2014-09-25
The present work demonstrates that NMR spin relaxation rate constants for molecules interconverting between states with different diffusion tensors can be modeled theoretically by combining orientational correlation functions for exchanging spherical molecules with locally isotropic approximations for the diffusion anisotropic tensors. The resulting expressions are validated by comparison with correlation functions obtained by Monte Carlo simulations and are accurate for moderate degrees of diffusion anisotropy typically encountered in investigations of globular proteins. The results are complementary to an elegant, but more complex, formalism that is accurate for all degrees of diffusion anisotropy [Ryabov, Y.; Clore, G. M.; Schwieters, C. D. J. Chem. Phys. 2012, 136, 034108]. PMID:25167331
Molecular structure-property correlations from optical nonlinearity and thermal-relaxation dynamics
Bhattacharyya, Indrajit; Priyadarshi, Shekhar; Goswami, Debabrata
2009-01-01
We apply ultrafast single beam Z-scan technique to measure saturation absorption coefficients and nonlinear-refraction coefficients of primary alcohols at 1560 nm. The nonlinear effects result from vibronic transitions and cubic nonlinear-refraction. To measure the pure total third-order nonlinear susceptibility, we removed thermal effects with a frequency optimized optical-chopper. Our measurements of thermal-relaxation dynamics of alcohols, from 1560 nm thermal lens pump and 780 nm probe ex...
Smith, Grant D.; Bedrov, Dmitry; Paul, Wolfgang
2004-09-01
The dynamic coherent structure factor Scoh(q,t) for a 1,4-polybutadiene (PBD) melt has been investigated using atomistic molecular dynamics simulations. The relaxation of Scoh(q,t) at q=1.44 Å-1 and q=2.72 Å-1, corresponding to the first and second peaks in the static structure factor for PBD, was studied in detail over a wide range of temperature. It was found that time-temperature superposition holds for the α-relaxation for both q values over a wide temperature range and that the α-relaxation can be well described by a stretched (Kohlrauch-William-Watts) exponential with temperature independent but q dependent amplitude and stretching exponent. The α-relaxation times for both q values were found to exhibit the same non-Arrhenius temperature dependence, indicating that the same physical processes are responsible for relaxation on both length scales. The α-relaxation time was found to depend strongly upon the dynamical range of data utilized in determining the relaxation time, accounting for qualitative discrepancies between α-relaxation times reported here and those extracted for PBD from experimentally measured Scoh(q,t).
Poirier-Brulez, Fabienne; Roudaut, Gaëlle; Champion, Dominique; Tanguy, Marie; Simatos, Denise
2006-02-01
Molecular mobility is known to be a key parameter in controlling the physical properties of materials and thus their quality and performance. Beyond glass transition related changes, attention should be called to the impact of local motions remaining in the glassy state. Gelatinized waxy maize starch at different sucrose contents (0-20% solids) was equilibrated between 0 and 14% water and sorption isotherms determined at 25 degrees C. The effect of water and sucrose content on the molecular mobility of glassy starch was investigated by differential scanning calorimetry through enthalpy relaxation studies and dynamical mechanical thermal analysis. The existence of sucrose-starch interactions was suggested by the sorption isotherms not following the expected additivity of the single component sorption curves. Contrary to the glass transition or associated alpha relaxation, water and sucrose affected differently the secondary relaxations. Indeed, the beta relaxation observed around -15 degrees C was shifted to lower temperature upon increasing hydration, and to higher temperature when sucrose content increased, suggesting a hindering of these local motions. Enthalpy relaxation of the ternary mixtures was studied following aging up to 668 h at Tg -15 degrees C. Ternary mixtures exhibited an enthalpy relaxation upon aging lower than starch alone as a sign of lower polymer mobility in the presence of small molecules, contrary to the free volume theory. Relaxation kinetics were characterized with the Cowie-Ferguson model and compared to literature data. The extent of the enthalpy relaxation appeared to be controlled by the distance between the aging temperature and the beta relaxation temperature. PMID:16127661
Accelerating molecular simulations of proteins using Bayesian inference on weak information
Perez, Alberto; MacCallum, Justin L.; Dill, Ken A.
2015-01-01
Atomistic molecular dynamics (MD) simulations of protein molecules are too computationally expensive to predict most native structures from amino acid sequences. Here, we integrate “weak” external knowledge into folding simulations to predict protein structures, given their sequence. For example, we instruct the computer “to form a hydrophobic core,” “to form good secondary structures,” or “to seek a compact state.” This kind of information has been too combinatoric, nonspecific, and vague to help guide MD simulations before. Within atomistic replica-exchange molecular dynamics (REMD), we develop a statistical mechanical framework, modeling using limited data with coarse physical insight(s) (MELD + CPI), for harnessing weak information. As a test, we apply MELD + CPI to predict the native structures of 20 small proteins. MELD + CPI samples to within less than 3.2 Å from native for all 20 and correctly chooses the native structures (<4 Å) for 15 of them, including ubiquitin, a millisecond folder. MELD + CPI is up to five orders of magnitude faster than brute-force MD, satisfies detailed balance, and should scale well to larger proteins. MELD + CPI may be useful where physics-based simulations are needed to study protein mechanisms and populations and where we have some heuristic or coarse physical knowledge about states of interest. PMID:26351667
Low-relaxation spin waves in laser-molecular-beam epitaxy grown nanosized yttrium iron garnet films
Lutsev, L. V.; Korovin, A. M.; Bursian, V. E.; Gastev, S. V.; Fedorov, V. V.; Suturin, S. M.; Sokolov, N. S.
2016-05-01
Synthesis of nanosized yttrium iron garnet (Y3Fe5O12, YIG) films followed by the study of ferromagnetic resonance (FMR) and spin wave propagation in these films is reported. The YIG films were grown on gadolinium gallium garnet substrates by laser molecular beam epitaxy. It has been shown that spin waves propagating in YIG deposited at 700 °C have low damping. At the frequency of 3.29 GHz, the spin-wave damping parameter is less than 3.6 × 10-5. Magnetic inhomogeneities of the YIG films give the main contribution to the FMR linewidth. The contribution of the relaxation processes to the FMR linewidth is as low as 1.2%.
Rheingold, Arnold L.; DiPasquale, Antonio G. [Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0358 (United States); Beckmann, Peter A. [Department of Physics, Bryn Mawr College, 101 North Merion Avenue, Bryn Mawr, PA 19010-2899 (United States)], E-mail: pbeckman@brynmawr.edu
2008-04-03
We correlate an X-ray determination of the molecular and crystal structures of 2-tert-butylanthracene and 2-tert-butylanthraquinone reported here with the previously reported dynamical nuclear magnetic resonance determination of the motions of the tert-butyl groups and their resident methyl groups in the solid state [P.A. Beckmann, K.S. Burbank, M.M.W. Lau, J.N. Ree, T.L. Weber, Chem. Phys. 290 (2003) 241].
We correlate an X-ray determination of the molecular and crystal structures of 2-tert-butylanthracene and 2-tert-butylanthraquinone reported here with the previously reported dynamical nuclear magnetic resonance determination of the motions of the tert-butyl groups and their resident methyl groups in the solid state [P.A. Beckmann, K.S. Burbank, M.M.W. Lau, J.N. Ree, T.L. Weber, Chem. Phys. 290 (2003) 241
Debashis Mukherjee
2002-06-01
Full Text Available Abstract: We present in this paper two new versions of Rayleigh-SchrÃ‚Â¨odinger (RS and the Brillouin-Wigner (BW state-specific multi-reference perturbative theories (SSMRPT which stem from our state-specific multi-reference coupled-cluster formalism (SS-MRCC, developed with a complete active space (CAS. They are manifestly sizeextensive and are designed to avoid intruders. The combining coefficients cÃŽÂ¼ for the model functions ÃÂ†ÃŽÂ¼ are completely relaxed and are obtained by diagonalizing an effective operator in the model space, one root of which is the target eigenvalue of interest. By invoking suitable partitioning of the hamiltonian, very convenient perturbative versions of the formalism in both the RS and the BW forms are developed for the second order energy. The unperturbed hamiltonians for these theories can be chosen to be of both MÃÂ†ller-Plesset (MP and Epstein-Nesbet (EN type. However, we choose the corresponding Fock operator fÃŽÂ¼ for each model function ÃÂ†ÃŽÂ¼, whose diagonal elements are used to define the unperturbed hamiltonian in the MP partition. In the EN partition, we additionally include all the diagonal direct and exchange ladders. Our SS-MRPT thus utilizes a multi-partitioning strategy. Illustrative numerical applications are presented for potential energy surfaces (PES of the ground (1ÃŽÂ£+ and the first delta (1ÃŽÂ” states of CH+ which possess pronounced multi-reference character. Comparison of the results with the corresponding full CI values indicates the efficacy of our formalisms.
Proton spin-lattice relaxation and molecular motion in solid dimethylsulphoxide
An NMR-25MHz pulse spectrometer, characterised by 4,0 μsec recovery time and 1,5 μsec π/2 pulse length, was constructed in our Laboratory. Measurements of proton spin-lattice relaxation times in solid DMSO were performed as a function of temperature down to 900K using 90-t-90 and 180-t-90 pulse sequences. LogT1 plotted versus reciprocal temperature exhibits two minima at 2200K and 1650K. Arrhenius behaviour of T1 enables to determine activation energies: 3,84 kcal/mol above 2200K; 2,95 kcal/mol below 1650K; and 4,36 kcal/ mol below 1100K. The results can be interpreted as evidence of non-equivalent motion of methyl groups, as revealed by the observed double minimum yielding the pre-exponential factors for correlation times 5.10-13sec and 6.10-13sec and confirmed by x-ray measurements suggesting a difference of 0,05 Angstroem in carbon-sulphur distances /Thomas, Shoemaker, Eriks/. Below 1100K, both methyl groups characterised by the same values of correlation times appear to be dynamically equivalent. Theoretical values of Tsub(1min), calculated for methyl groups reorienting about the C3 axis and coupled via dipole-dipole interaction, are in good agreement with experiment. The intermolecular contribution is negligible from measurements performed for deuterated solutions. The present measurement of T1 do not suggest an overall tumbling of molecues in the experimental conditions. (author)
Trerayapiwat, Kasidet; Ricke, Nathan; Cohen, Peter; Poblete, Alex; Rudel, Holly; Eustis, Soren N
2016-08-10
This work explores the relationship between theoretically predicted excitation energies and experimental molar absorption spectra as they pertain to environmental aquatic photochemistry. An overview of pertinent Quantum Chemical descriptions of sunlight-driven electronic transitions in organic pollutants is presented. Second, a combined molecular dynamics (MD), time-dependent density functional theory (TD-DFT) analysis of the ultraviolet to visible (UV-Vis) absorption spectra of six model organic compounds is presented alongside accurate experimental data. The functional relationship between the experimentally observed molar absorption spectrum and the discrete quantum transitions is examined. A rigorous comparison of the accuracy of the theoretical transition energies (ΔES0→Sn) and oscillator strength (fS0→Sn) is afforded by the probabilistic convolution and deconvolution procedure described. This method of deconvolution of experimental spectra using a Gaussian Mixture Model combined with Bayesian Information Criteria (BIC) to determine the mean (μ) and standard deviation (σ) as well as the number of observed singlet to singlet transition energy state distributions. This procedure allows a direct comparison of the one-electron (quantum) transitions that are the result of quantum chemical calculations and the ensemble of non-adiabatic quantum states that produce the macroscopic effect of a molar absorption spectrum. Poor agreement between the vertical excitation energies produced from TD-DFT calculations with five different functionals (CAM-B3LYP, PBE0, M06-2X, BP86, and LC-BLYP) suggest a failure of the theory to capture the low energy, environmentally important, electronic transitions in our model organic pollutants. However, the method of explicit-solvation of the organic solute using the quantum Effective Fragment Potential (EFP) in a density functional molecular dynamics trajectory simulation shows promise as a robust model of the hydrated organic
Practical theoretical methods are developed and implemented for handling molecular collision problems and subsequently a study was made of the important processes which influence collision rates and a computation made of rate information suitable for gas laser and combustion kinetics modeling studies. The study focuses on CO and HF molecules, which are of practical interest as molecular lasers and of theoretical interest for discerning the role of rotation processes in vibrational relaxation. 26 references
Progress in the study of molecular organized assemblies by dielectric relaxation spectroscopy
无
2006-01-01
Because dielectric spectroscopy covers a great many problems in physical and chemical systems occurring in an extremely wide frequency range, the study of this method plays an important role in physical chemistry. As an effective tool to detect inner properties of substance systems, the dielectric spectroscopy method is widely used in chemical systems and has been dramatically developed in recent decade. This review paper describes the applications of the dielectric spectroscopy in the chemical field, and main concentrations are focused on the micelle, microemulsion and other so-called molecular organized assemblies. Some dielectric principles and models proposed for these systems are introduced. In addition, recent technical developments in dielectric spectroscopy and developing trend of this method in other chemical systems are reviewed.
Inferring Genotype of DNA Molecular Marker by Bayesian Theorem%应用贝叶斯理论推断DNA分子标记基因型
莫惠栋; 姜长鉴
2002-01-01
引入贝叶斯理论用以从DNA分子标记的表现型(电泳谱带)推断其基因型(DNA来源).结果表明,根据标记座位独立假定而确定的遗传信息不完全标记的基因型概率,与根据邻近的遗传信息完全标记的基因型和有关重组率算得的相应贝叶斯概率,通常都有很大的差异.所以在进行数量性状基因定位和标记辅助选择等工作之前,应当计算每一个体基因组上所有遗传信息不完全座位的有关基因型的贝叶斯概率.文中列出计算未知基因型的贝叶斯概率的详细过程,也讨论了贝叶斯概率的若干推广应用.%Bayesian theorem is applied to infer the DNA molecular marker genotype(DNA chain type) from its phenotype (electrophoresis band type). The results indicated that large differences often present in the genotype probability of a molecular marker with incomplete genetic information when it is obtained from the assumption of independence among markers as compared with that inferred from the genotypes of the flanking markers with the complete genetic information and the recombination fractions among them based on the Bayesian theorem. Therefore, before utilizing the marker information, such as in mapping quantitative trait loci (QTL), marker assisted selection (MAS) etc., Bayesian probability of the genotype for all markers with incomplete genetic information must be calculated over the whole genome for every individual. This study provides detailed procedure for the calculation of the Bayesian probability of the unknown genotype. Several extensions were also discussed for the application of the Bayesian theorem.
Influence of the Ge layer thickness and annealing conditions on the parameters of relaxed Ge/Si(001) layers grown by molecular beam epitaxy via two-stage growth is investigated. The dependences of the threading dislocation density and surface roughness on the Ge layer thickness, annealing temperature and time, and the presence of a hydrogen atmosphere are obtained. As a result of optimization of the growth and annealing conditions, relaxed Ge/Si(001) layers which are thinner than 1 μm with a low threading dislocation density on the order of 107 cm–2 and a root mean square roughness of less than 1 nm are obtained
Total cross sections for the positive and negative fragments resulting from dissociative collisions with He of vibrationally relaxed H3+, D3+, and HD2+ molecular ions have been measured in the energy range 3-9.8 keV. The measured absolute total-cross-section values are more than one order of magnitude smaller than those previously reported with the molecular ions without vibrational relaxation. When the cross sections are plotted as a function of the projectile speed and normalized to compensate for the relative fragment yield, the values for the production of deuterium fragments are higher than those for hydrogen ions in the energy range of the present study. These results are consistent with the theoretical predictions for the behavior of triatomic molecular ions with high rovibrational excitation
Baranowski, M.; Woźniak-Braszak, A.; Jurga, K.
2016-01-01
The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins 1H are polarized in the magnetic field B0 while fluorine spins 19F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.
Allen, Jesse J; Bowser, Sage R; Damodaran, Krishnan
2014-05-01
Interactions of ionic liquids (ILs) with water are of great interest for many potential IL applications. 1-Ethyl-3-methylimidazolium (emim) acetate, in particular, has shown interesting interactions with water including hydrogen bonding and even chemical exchange. Previous studies have shown the unusual behavior of emim acetate when in the presence of 0.43 mole fraction of water, and a combination of NMR techniques is used herein to investigate the emim acetate-water system and the unusual behavior at 0.43 mole fraction of water. NMR relaxometry techniques are used to describe the effects of water on the molecular motion and interactions of emim acetate with water. A discontinuity is seen in nuclear relaxation behavior at the concentration of 0.43 mole fraction of water, and this is attributed to the formation of a hydrogen bonded network. EXSY measurements are used to determine the exchange rates between the H2 emim proton and water, which show a complex dependence on the concentration of the mixture. The findings support and expand our previous results, which suggested the presence of an extended hydrogen bonding network in the emim acetate-water system at concentrations close to 0.50 mole fraction of H2O. PMID:24654003
Lesaffre, Emmanuel
2012-01-01
The growth of biostatistics has been phenomenal in recent years and has been marked by considerable technical innovation in both methodology and computational practicality. One area that has experienced significant growth is Bayesian methods. The growing use of Bayesian methodology has taken place partly due to an increasing number of practitioners valuing the Bayesian paradigm as matching that of scientific discovery. In addition, computational advances have allowed for more complex models to be fitted routinely to realistic data sets. Through examples, exercises and a combination of introd
Arosio, Paolo, E-mail: paolo.arosio@guest.unimi.it; Orsini, Francesco [Department of Physics, Università degli Studi di Milano, and INSTM, Milano (Italy); Corti, Maurizio [Department of Physics, Università degli Studi di Pavia and INSTM, Pavia (Italy); Mariani, Manuel [Department of Physics and Astronomy, Università degli Studi di Bologna, Bologna (Italy); Bogani, Lapo [Physikalisches Institut, Universität Stuttgart, Stuttgart (Germany); Caneschi, Andrea [INSTM and Department of Chemistry, University of Florence, Firenze (Italy); Lago, Jorge [Departamento de Quimica Inorganica, Universidad del Pais Vasco, Bilbao (Spain); Lascialfari, Alessandro [Department of Physics, Università degli Studi di Milano, and INSTM, Milano (Italy); Centro S3, Istituto Nanoscienze - CNR, Modena (Italy)
2015-05-07
The spin dynamics of the molecular magnetic chain [Dy(hfac){sub 3}(NIT(C{sub 6}H{sub 4}OPh))] were investigated by means of the Muon Spin Relaxation (μ{sup +}SR) technique. This system consists of a magnetic lattice of alternating Dy(III) ions and radical spins, and exhibits single-chain-magnet behavior. The magnetic properties of [Dy(hfac){sub 3}(NIT(C{sub 6}H{sub 4}OPh))] have been studied by measuring the magnetization vs. temperature at different applied magnetic fields (H = 5, 3500, and 16500 Oe) and by performing μ{sup +}SR experiments vs. temperature in zero field and in a longitudinal applied magnetic field H = 3500 Oe. The muon asymmetry P(t) was fitted by the sum of three components, two stretched-exponential decays with fast and intermediate relaxation times, and a third slow exponential decay. The temperature dependence of the spin dynamics has been determined by analyzing the muon longitudinal relaxation rate λ{sub interm}(T), associated with the intermediate relaxing component. The experimental λ{sub interm}(T) data were fitted with a corrected phenomenological Bloembergen-Purcell-Pound law by using a distribution of thermally activated correlation times, which average to τ = τ{sub 0} exp(Δ/k{sub B}T), corresponding to a distribution of energy barriers Δ. The correlation times can be associated with the spin freezing that occurs when the system condenses in the ground state.
Draper, D.
2001-01-01
© 2012 Springer Science+Business Media, LLC. All rights reserved. Article Outline: Glossary Definition of the Subject and Introduction The Bayesian Statistical Paradigm Three Examples Comparison with the Frequentist Statistical Paradigm Future Directions Bibliography
Relaxation phenomena in disordered systems
Sciortino, F.; Tartaglia, P.
1997-02-01
In this article we discuss how the assumptions of self-similarity imposed on the distribution of independently relaxing modes, as well as on their amplitude and characteristic times, manifest in the global relaxation phenomena. We also review recent applications of such approach to the description of relaxation phenomena in microemulsions and molecular glasses.
Prévot, G.; Cohen, C.; Schmaus, D.; Hecquet, P.; Salanon, B.
2002-05-01
We have studied the relaxations and vibrations of atoms near the surface of a (1,1,19) copper crystal. For this purpose, we have performed molecular dynamics simulations using a semi-empirical many-body potential derived from tight binding models. The total displacement field can be described as the sum of a mean surface relaxation and a specific contribution of the steps, which is maximal for step edge atoms (0.08 Å) and corner atoms (0.06 Å). Whereas step edge atoms relax towards the inner terrace and towards the bulk, corner atoms relax in the opposite direction, leading to vortex-like structures in the displacement field. We demonstrate that, as predicted by continuous elasticity, the displacement field induced by steps is equivalent to the one created by a line of dipoles on a flat surface. In the particular case studied here, the equivalent dipole density is 3.3×10 -10 N. The specific relaxations of kink atoms have been calculated. We have also studied the variation of the relaxations as a function of temperature ( T). A strong effect is predicted for inner terrace atoms: when increasing T, the contraction of the first interplanar distance, with respect to the bulk value, progressively cancels and turns to an expansion at high T. This is not the case for the specific contraction of step edge atoms that is nearly temperature independent. This latter behaviour is related to very strong longitudinal correlation between vibrations of the step edge atom and of its nearest neighbour inside the terrace. In the same time, whereas the vibrations of inner terrace atoms are found to be isotropic, the ones of step edge atoms are anisotropic, with a larger component along the direction parallel to the terrace plane and perpendicular to the step edge, the other components being the same as for inner terrace atoms.
Strain relaxation in GaN/AlxGa1-xN superlattices grown by plasma-assisted molecular-beam epitaxy
We have investigated the misfit relaxation process in GaN/AlxGa1-xN (x = 0.1, 0.3, 0.44) superlattices (SL) deposited by plasma-assisted molecular beam epitaxy. The SLs under consideration were designed to achieve intersubband absorption in the mid-infrared spectral range. We have considered the case of growth on GaN (tensile stress) and on AlGaN (compressive stress) buffer layers, both deposited on GaN-on-sapphire templates. Using GaN buffer layers, the SL remains almost pseudomorphic for x = 0.1, 0.3, with edge-type threading dislocation densities below 9 x 108 cm-2 to 2 x 109 cm-2. Increasing the Al mole fraction to 0.44, we observe an enhancement of misfit relaxation resulting in dislocation densities above 1010 cm-2. In the case of growth on AlGaN, strain relaxation is systematically stronger, with the corresponding increase in the dislocation density. In addition to the average relaxation trend of the SL, in situ measurements indicate a periodic fluctuation of the in-plane lattice parameter, which is explained by the different elastic response of the GaN and AlGaN surfaces to the Ga excess at the growth front. The results are compared with GaN/AlN SLs designed for near-infrared intersubband absorption.
Graphical abstract: Picosecond IR-UV pump–probe study revealed a detailed energy dissipation route and its time scale from the energy put into the OH(OD) stretching vibration for the phenol–water hydrogen-bonded complex. - Abstract: A comparative study of vibrational energy relaxation (VER) between the monohydrated complexes of phenol-d0 and phenol-d1 is investigated in a supersonic molecular beam. The direct time-resolved measurement of energy redistribution from the phenolic OH/OD stretching mode of the phenol-d0-H2O/phenol-d1-D2O is performed by picosecond IR-UV pump–probe spectroscopy. Two complexes follow the same relaxation process that begins with the intramolecular vibrational energy redistribution (IVR) and the intermolecular vibrational energy redistribution (IVR), which is followed by the vibrational predissociation (VP). The difference in the relaxation lifetimes between them is discussed by anharmonic force field and RRKM calculations. Anharmonic analysis implies that intra- (IVR) and intermolecular (IVR) relaxations occur in parallel in the complexes. The RRKM-predicted dissociation (VP) lifetimes show qualitative agreement with the observed results, suggesting that VP takes place after the statistical energy distribution in the complexes
BEAST: Bayesian evolutionary analysis by sampling trees
Drummond Alexei J
2007-11-01
Full Text Available Abstract Background The evolutionary analysis of molecular sequence variation is a statistical enterprise. This is reflected in the increased use of probabilistic models for phylogenetic inference, multiple sequence alignment, and molecular population genetics. Here we present BEAST: a fast, flexible software architecture for Bayesian analysis of molecular sequences related by an evolutionary tree. A large number of popular stochastic models of sequence evolution are provided and tree-based models suitable for both within- and between-species sequence data are implemented. Results BEAST version 1.4.6 consists of 81000 lines of Java source code, 779 classes and 81 packages. It provides models for DNA and protein sequence evolution, highly parametric coalescent analysis, relaxed clock phylogenetics, non-contemporaneous sequence data, statistical alignment and a wide range of options for prior distributions. BEAST source code is object-oriented, modular in design and freely available at http://beast-mcmc.googlecode.com/ under the GNU LGPL license. Conclusion BEAST is a powerful and flexible evolutionary analysis package for molecular sequence variation. It also provides a resource for the further development of new models and statistical methods of evolutionary analysis.
Yurasov, D. V., E-mail: Inquisitor@ipm.sci-nnov.ru [Russian Academy of Sciences, Institute for Physics of Microstructures (Russian Federation); Bobrov, A. I. [Lobachevsky State University of Nizhny Novgorod (Russian Federation); Daniltsev, V. M.; Novikov, A. V. [Russian Academy of Sciences, Institute for Physics of Microstructures (Russian Federation); Pavlov, D. A. [Lobachevsky State University of Nizhny Novgorod (Russian Federation); Skorokhodov, E. V.; Shaleev, M. V.; Yunin, P. A. [Russian Academy of Sciences, Institute for Physics of Microstructures (Russian Federation)
2015-11-15
Influence of the Ge layer thickness and annealing conditions on the parameters of relaxed Ge/Si(001) layers grown by molecular beam epitaxy via two-stage growth is investigated. The dependences of the threading dislocation density and surface roughness on the Ge layer thickness, annealing temperature and time, and the presence of a hydrogen atmosphere are obtained. As a result of optimization of the growth and annealing conditions, relaxed Ge/Si(001) layers which are thinner than 1 μm with a low threading dislocation density on the order of 10{sup 7} cm{sup –2} and a root mean square roughness of less than 1 nm are obtained.
Bayesian non- and semi-parametric methods and applications
Rossi, Peter
2014-01-01
This book reviews and develops Bayesian non-parametric and semi-parametric methods for applications in microeconometrics and quantitative marketing. Most econometric models used in microeconomics and marketing applications involve arbitrary distributional assumptions. As more data becomes available, a natural desire to provide methods that relax these assumptions arises. Peter Rossi advocates a Bayesian approach in which specific distributional assumptions are replaced with more flexible distributions based on mixtures of normals. The Bayesian approach can use either a large but fixed number
RELAX: detecting relaxed selection in a phylogenetic framework.
Wertheim, Joel O; Murrell, Ben; Smith, Martin D; Kosakovsky Pond, Sergei L; Scheffler, Konrad
2015-03-01
Relaxation of selective strength, manifested as a reduction in the efficiency or intensity of natural selection, can drive evolutionary innovation and presage lineage extinction or loss of function. Mechanisms through which selection can be relaxed range from the removal of an existing selective constraint to a reduction in effective population size. Standard methods for estimating the strength and extent of purifying or positive selection from molecular sequence data are not suitable for detecting relaxed selection, because they lack power and can mistake an increase in the intensity of positive selection for relaxation of both purifying and positive selection. Here, we present a general hypothesis testing framework (RELAX) for detecting relaxed selection in a codon-based phylogenetic framework. Given two subsets of branches in a phylogeny, RELAX can determine whether selective strength was relaxed or intensified in one of these subsets relative to the other. We establish the validity of our test via simulations and show that it can distinguish between increased positive selection and a relaxation of selective strength. We also demonstrate the power of RELAX in a variety of biological scenarios where relaxation of selection has been hypothesized or demonstrated previously. We find that obligate and facultative γ-proteobacteria endosymbionts of insects are under relaxed selection compared with their free-living relatives and obligate endosymbionts are under relaxed selection compared with facultative endosymbionts. Selective strength is also relaxed in asexual Daphnia pulex lineages, compared with sexual lineages. Endogenous, nonfunctional, bornavirus-like elements are found to be under relaxed selection compared with exogenous Borna viruses. Finally, selection on the short-wavelength sensitive, SWS1, opsin genes in echolocating and nonecholocating bats is relaxed only in lineages in which this gene underwent pseudogenization; however, selection on the functional
Kirstein, Roland
2005-01-01
This paper presents a modification of the inspection game: The ?Bayesian Monitoring? model rests on the assumption that judges are interested in enforcing compliant behavior and making correct decisions. They may base their judgements on an informative but imperfect signal which can be generated costlessly. In the original inspection game, monitoring is costly and generates a perfectly informative signal. While the inspection game has only one mixed strategy equilibrium, three Perfect Bayesia...
Beckmann, Peter A.; Rheingold, Arnold L.
2016-04-01
The dynamics of methyl (CH3) and fluoromethyl (CF3) groups in organic molecular (van der Waals) solids can be exploited to survey their local environments. We report solid state 1H and 19F spin-lattice relaxation experiments in polycrystalline 3-trifluoromethoxycinnamic acid, along with an X-ray diffraction determination of the molecular and crystal structure, to investigate the intramolecular and intermolecular interactions that determine the properties that characterize the CF3 reorientation. The molecule is of no particular interest; it simply provides a motionless backbone (on the nuclear magnetic resonance (NMR) time scale) to investigate CF3 reorientation occurring on the NMR time scale. The effects of 19F-19F and 19F-1H spin-spin dipolar interactions on the complicated nonexponential NMR relaxation provide independent inputs into determining a model for CF3 reorientation. As such, these experiments provide much more information than when only one spin species (usually 1H) is present. In Sec. IV, which can be read immediately after the Introduction without reading the rest of the paper, we compare the barrier to CH3 and CF3 reorientation in seven organic solids and separate this barrier into intramolecular and intermolecular components.
Simon Boitard
2016-03-01
Full Text Available Inferring the ancestral dynamics of effective population size is a long-standing question in population genetics, which can now be tackled much more accurately thanks to the massive genomic data available in many species. Several promising methods that take advantage of whole-genome sequences have been recently developed in this context. However, they can only be applied to rather small samples, which limits their ability to estimate recent population size history. Besides, they can be very sensitive to sequencing or phasing errors. Here we introduce a new approximate Bayesian computation approach named PopSizeABC that allows estimating the evolution of the effective population size through time, using a large sample of complete genomes. This sample is summarized using the folded allele frequency spectrum and the average zygotic linkage disequilibrium at different bins of physical distance, two classes of statistics that are widely used in population genetics and can be easily computed from unphased and unpolarized SNP data. Our approach provides accurate estimations of past population sizes, from the very first generations before present back to the expected time to the most recent common ancestor of the sample, as shown by simulations under a wide range of demographic scenarios. When applied to samples of 15 or 25 complete genomes in four cattle breeds (Angus, Fleckvieh, Holstein and Jersey, PopSizeABC revealed a series of population declines, related to historical events such as domestication or modern breed creation. We further highlight that our approach is robust to sequencing errors, provided summary statistics are computed from SNPs with common alleles.
The conundrum of relaxation times
The current theories of proton relaxation times fall short of explaining satisfactorily the physical and biological mechanisms responsible for the dissimilarities of relaxation behavior in normal and pathological tissues. An alternative approach to understand these mechanisms is needed. This paper advances the possibility that the dissimilarities of relaxation behavior in normal and pathological tissues is due to the consumption of paramagnetic molecular O2 dissolved in cell-associated water. (orig.)
Simkovitch, R.; Akulov, K.; Erez, Y.; Amdursky, N.; Gepshtein, R.; Schwartz, T.; Huppert, D.
2015-09-01
Steady-state and time-resolved UV-Vis spectroscopy techniques were employed to study the non-radiative process of Auramine-O (AuO). We focused our attention on the ultrafast nonradiative decay of Auramine-O in water and on the acid effect on Auramine-O spectroscopy. We found that weak acids like formic acid shorten the excited-state decay times of both the emission and the transient pump-probe spectra of Auramine-O. We found three time domains in the relaxation of the excited states back to the ground state. In mixtures of acetic and formic acids, the three decay times associated with the relaxation process are shorter in the presence of formic acid in Auramine-O solutions. We qualitatively explain the very large non-radiative rate in water and in formic-acetic acid mixtures by a protic nonradiative model proposed by Sobolewski and Domcke. The steady-state emission spectrum of AuO adsorbed on insulin fibrils consists of two bands assigned to protonated and deprotonated forms and the emission intensity increases by three orders of magnitude. We conclude that the nonradiative process prevails in the liquid state, whereas when AuO is adsorbed on fibrils the nonradiative rate is reduced by three orders of magnitude and thus enables a slow ESPT process to occur.
Bessiere, Pierre; Ahuactzin, Juan Manuel; Mekhnacha, Kamel
2013-01-01
Probability as an Alternative to Boolean LogicWhile logic is the mathematical foundation of rational reasoning and the fundamental principle of computing, it is restricted to problems where information is both complete and certain. However, many real-world problems, from financial investments to email filtering, are incomplete or uncertain in nature. Probability theory and Bayesian computing together provide an alternative framework to deal with incomplete and uncertain data. Decision-Making Tools and Methods for Incomplete and Uncertain DataEmphasizing probability as an alternative to Boolean
Sérgio L. Pereira
2008-01-01
Full Text Available Most Neotropical birds, including Pteroglossus aracaris, do not have an adequate fossil record to be used as time constraints in molecular dating. Hence, the evolutionary timeframe of the avian biota can only be inferred using alternative time constraints. We applied a Bayesian relaxed clock approach to propose an alternative interpretation for the historical biogeography of Pteroglossus based on mitochondrial DNA sequences, using different combinations of outgroups and time constraints obtained from outgroup fossils, vicariant barriers and molecular time estimates. The results indicated that outgroup choice has little effect on the Bayesian posterior distribution of divergence times within Pteroglossus , that geological and molecular time constraints seem equally suitable to estimate the Bayesian posterior distribution of divergence times for Pteroglossus , and that the fossil record alone overestimates divergence times within the fossil-lacking ingroup. The Bayesian estimates of divergence times suggest that the radiation of Pteroglossus occurred from the Late Miocene to the Pliocene (three times older than estimated by the “standard” mitochondrial rate of 2% sequence divergence per million years, likely triggered by Andean uplift, multiple episodes of marine transgressions in South America, and formation of present-day river basins. The time estimates are in agreement with other Neotropical taxa with similar geographic distributions.
Das, Anuradha; Das, Suman; Biswas, Ranjit, E-mail: ranjit@bose.res.in [Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata, West Bengal 700098 (India)
2015-01-21
Temperature dependent relaxation dynamics, particle motion characteristics, and heterogeneity aspects of deep eutectic solvents (DESs) made of acetamide (CH{sub 3}CONH{sub 2}) and urea (NH{sub 2}CONH{sub 2}) have been investigated by employing time-resolved fluorescence measurements and all-atom molecular dynamics simulations. Three different compositions (f) for the mixture [fCH{sub 3}CONH{sub 2} + (1 − f)NH{sub 2}CONH{sub 2}] have been studied in a temperature range of 328-353 K which is ∼120-145 K above the measured glass transition temperatures (∼207 K) of these DESs but much lower than the individual melting temperature of either of the constituents. Steady state fluorescence emission measurements using probe solutes with sharply different lifetimes do not indicate any dependence on excitation wavelength in these metastable molten systems. Time-resolved fluorescence anisotropy measurements reveal near-hydrodynamic coupling between medium viscosity and rotation of a dissolved dipolar solute. Stokes shift dynamics have been found to be too fast to be detected by the time-resolution (∼70 ps) employed, suggesting extremely rapid medium polarization relaxation. All-atom simulations reveal Gaussian distribution for particle displacements and van Hove correlations, and significant overlap between non-Gaussian (α{sub 2}) and new non-Gaussian (γ) heterogeneity parameters. In addition, no stretched exponential relaxations have been detected in the simulated wavenumber dependent acetamide dynamic structure factors. All these results are in sharp contrast to earlier observations for ionic deep eutectics with acetamide [Guchhait et al., J. Chem. Phys. 140, 104514 (2014)] and suggest a fundamental difference in interaction and dynamics between ionic and non-ionic deep eutectic solvent systems.
Relaxed Poisson cure rate models.
Rodrigues, Josemar; Cordeiro, Gauss M; Cancho, Vicente G; Balakrishnan, N
2016-03-01
The purpose of this article is to make the standard promotion cure rate model (Yakovlev and Tsodikov, ) more flexible by assuming that the number of lesions or altered cells after a treatment follows a fractional Poisson distribution (Laskin, ). It is proved that the well-known Mittag-Leffler relaxation function (Berberan-Santos, ) is a simple way to obtain a new cure rate model that is a compromise between the promotion and geometric cure rate models allowing for superdispersion. So, the relaxed cure rate model developed here can be considered as a natural and less restrictive extension of the popular Poisson cure rate model at the cost of an additional parameter, but a competitor to negative-binomial cure rate models (Rodrigues et al., ). Some mathematical properties of a proper relaxed Poisson density are explored. A simulation study and an illustration of the proposed cure rate model from the Bayesian point of view are finally presented. PMID:26686485
In glass-forming melts the decay of structural fluctuation shows the well known transition from beta-relaxation (von-Schweidler law with exponent b) to alpha-decay (KWW law with exponent beta). Here we present results from molecular dynamics simulations for a metallic glass forming Ni0.5Zr0.5 model aimed at giving an understanding of this transition on the atomistic scale. At the considered temperature below mode coupling Tc, the dynamics of the system can be interpreted by residence of the particles in their neighbour cages and escape from the cages as rare processes. Our analysis yields that the fraction of residing particles is characterized by a hierarchical law in time, with von-Schweidler b explicitly related to the exponent of this law. In the alpha-decay regime the stretching exponent reflects, in addition, floating of the cages due to strain effects of escaped particles. Accordingly, the change from beta-relaxation to alpha-decay indicates the transition from low to large fraction of escaped particles.
Dielectric relaxation measurements carried out in nematic BOAOB reveal fast reorientational motions of the whole molecule around the long axis (τ1 ∼ 60 ps) as well as slow reorientational motions of the whole molecule around the short axis (τ1 ∼ 10-8 s). Incoherent quasielastic neutron scattering spectra obtained for nematic BOAOB, with normal and deuterated alkoxy terminals, are inpterpreted as dominated by reorientations (around the C-N bonds) of moieties consisting of benzene rings coupled with alkoxy terminals (τ1 ∼ 4 ps). In addition fast conformational changes occur in the terminals. Dielectric relaxation measurements reveal librations of the whole molecule in phases Cr 1 and Cr 2 accompanied by reorientation of the terminal groups in these phases. The reorientations occur in the time scale amounting to 10-8 s. Incoherent quasielastic neutron scattering spectra obtained for Cr 1 and Cr 2 phases of BOAOB were interpreted as dominated by overdamped librational motions of the moieties accompanied by fast conformational changes in the terminals. Cr 3 phase corresponds to a normal molecular crystal. 22 refs., 8 figs., 4 tabs. (author)
Dassler, K.; Roohi, F.; Lohrke, J.; Pison, U.; Ide, A.; Remmele, S.; Hütter, H.; Pietsch, H.; Schütz, G.
2012-01-01
The aim of our preclinical study was to investigate the minimum requirements for obtaining sensitive molecular MRI for use in tumor evaluations under optimal conditions. The well-vascularized F9 teratocarcinoma tumor model, which exhibits high levels of the highly accessible target CD105/endoglin, w
Gonzalez, Luis E.; Gonzalez, David J
2006-01-01
We have performed orbital free ab initio molecular dynamics simulations in order to study the thermal behaviour of two open surfaces of solid metallic systems, namely the (110) face of fcc Al and the (10-10) face of hcp Mg. Our results reproduce qualitatively both the experimental measurements and previous ab initio calculations performed with the more costly Kohn-Sham approach of Density Functional Theory. These calculations can be viewed as a validation test of the orbital free method for s...
Bayesian artificial intelligence
Korb, Kevin B
2010-01-01
Updated and expanded, Bayesian Artificial Intelligence, Second Edition provides a practical and accessible introduction to the main concepts, foundation, and applications of Bayesian networks. It focuses on both the causal discovery of networks and Bayesian inference procedures. Adopting a causal interpretation of Bayesian networks, the authors discuss the use of Bayesian networks for causal modeling. They also draw on their own applied research to illustrate various applications of the technology.New to the Second EditionNew chapter on Bayesian network classifiersNew section on object-oriente
Jensen, Finn Verner; Nielsen, Thomas Dyhre
2016-01-01
Mathematically, a Bayesian graphical model is a compact representation of the joint probability distribution for a set of variables. The most frequently used type of Bayesian graphical models are Bayesian networks. The structural part of a Bayesian graphical model is a graph consisting of nodes and...... largely due to the availability of efficient inference algorithms for answering probabilistic queries about the states of the variables in the network. Furthermore, to support the construction of Bayesian network models, learning algorithms are also available. We give an overview of the Bayesian network...
Daniela Becker
2008-09-01
Full Text Available Blendas de poliamida amorfa (aPA com copolímero de estireno-acrilonitrila (SAN utilizando uma série de copolímeros de metil metacrilato-anidrido maleico (MMA-MA como agente compatibilizante foram preparadas. Estes copolímeros acrílicos são miscíveis com a fase SAN, e o anidrido maleico (MA é capaz de reagir com os grupos terminais da poliamida, levando a formação de um copolímero na interfase da blenda durante o processamento. Este estudo foca o efeito da massa molar e a concentração de anidrido maleico do compatibilizante nas propriedades de relaxação dielétrica. Os resultados mostram que tanto a concentração de anidrido maleico e a massa molar do compatibilizante influenciam a mobilidade molecular. Blendas com compatibilizantes com 5 e 10% de anidrido maleico apresentaram menor energia de ativação devido à alta mobilidade da fase SAN.Blends of amorphous polyamide (aPA with acrylonitrile/styrene copolymer (SAN using a series of methyl methacrylate-maleic anhydride (MMA-MA copolymers as compatibilizing agents were prepared. These acrylic copolymers were miscible with SAN, whereas the maleic anhydride units in the copolymers are capable to react with the polyamide end groups; this could lead to the formation of grafted copolymers at the blend interface during melt processing. This study focuses on the effects of molecular weight and concentration of the reactive maleic anhydride units of the compatibilizer on the dielectric relaxation properties. The results show that both maleic anhydride quantity and molecular weight of MMA MA influenced the dielectric relaxation properties. Blends with 5 and 10% of MA in the compatibilizer present lower activation energy due to the high mobility of SAN phase.
A joint study of the rotational dynamics and free volume in amorphous 1-propanol (1-PrOH) as a prototypical monohydroxy alcohol by electron spin resonance (ESR) or positron annihilation lifetime spectroscopy (PALS), respectively, is reported. The dynamic parameters of the molecular spin probe 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and the annihilation ones of the atomic ortho-positronium (o-Ps) probe as a function of temperature are compared. A number of coincidences between various effects in the ESR and PALS responses at the corresponding characteristic ESR and PALS temperatures were found suggesting a common origin of the underlying dynamic processes that were identified using viscosity (VISC) in terms of the two-order parameter (TOP) model and broadband dielectric spectroscopy (BDS) data. (paper)
Andreozzi, L; Faetti, M; Giordano, M; Palazzuoli, D [Dipartimento di Fisica, Universita di Pisa, via F Buonarroti 2 Pisa I-56127, Italy and INFM, UdR Pisa, Italy (Italy)
2003-03-26
The enthalpy recovery mechanism of a low molecular weight synthesis of polymethylmethacrylate is investigated by means of differential scanning calorimetry (DSC) experiments. The experimental results can be described satisfactorily in terms of the Tool-Narayanaswamy-Moynihan theory. This work is mainly focused on developing a strategy for evaluation of the best set of parameters for the model. The approach starts with a simultaneous fitting procedure of several experimental DSC traces. Sets of parameters are obtained which exhibit agreement with experiments. The enthalpy lost on ageing of the sample in the glassy state as a function of the annealing time is then compared with the predictions provided by using the different sets of parameters. We show that this procedure is able to single out the best set of parameters and to provide a good estimation of the Adam-Gibbs temperature.
On polyhedral approximations of polytopes for learning Bayesian networks
Studený, Milan; Haws, D.C.
2013-01-01
Roč. 4, č. 1 (2013), s. 59-92. ISSN 1309-3452 R&D Projects: GA ČR GA201/08/0539 Institutional support: RVO:67985556 Keywords : Bayesian network structure * integer programming * standard imset * characteristic imset * LP relaxation Subject RIV: BA - General Mathematics http://library.utia.cas.cz/separaty/2013/MTR/studeny-on polyhedral approximations of polytopes for learning bayesian networks.pdf
RELAX: Detecting Relaxed Selection in a Phylogenetic Framework
Wertheim, Joel O; Murrell, Ben; Smith, Martin D.; Kosakovsky Pond, Sergei L; Scheffler, Konrad
2014-01-01
Relaxation of selective strength, manifested as a reduction in the efficiency or intensity of natural selection, can drive evolutionary innovation and presage lineage extinction or loss of function. Mechanisms through which selection can be relaxed range from the removal of an existing selective constraint to a reduction in effective population size. Standard methods for estimating the strength and extent of purifying or positive selection from molecular sequence data are not suitable for det...
The formation of H2 in the interstellar medium, from two hydrogen atoms, is a fundamental question in astrophysics. This very exothermic reaction is indeed the first step of a series of essential reactions for the interstellar physical-chemistry that takes place on the surface of interstellar dust grains. In the warm regions of the ISM, diffuse clouds and Photodissociation regions, the invoked formation mechanism is the Eley-Rideal heterogeneous catalysis reaction, in which one H atom is initially chemisorbed. The grains have mainly carbonaceous graphitic-like composition. Previous theoretical works carried out using constrained geometries were unable to explain the formation of H2 in the observed rovibrationnal states (v≤5). In order to take into account the degrees of freedom of all relevant atoms, we have built, from the Brenner potential, a new potential that models the graphene H-H system.With this potential, we have completed a classical molecular dynamics study of the formation of H2. This work has been performed for collision energies of the impinging H atoms from 0.015 eV to 0.2 eV and for surface temperature of 0, 10 and 30 K. One of the salient results is that the reaction cross section is directly related with the shape of the potential seen by the impinging H atom. Furthermore, the rovibrationnal distribution obtained by allowing the surface atoms to move is in better agreement with the one observed by astrophysicists (v≤6), the surface absorbs a large part (∼25%) of the available energy. Some works about the influence of: an additional H atom upon the surface or a possible porous structure of the grains, on the formation of H2 are presented in appendices. (author)
Gelman, Andrew; Stern, Hal S; Dunson, David B; Vehtari, Aki; Rubin, Donald B
2013-01-01
FUNDAMENTALS OF BAYESIAN INFERENCEProbability and InferenceSingle-Parameter Models Introduction to Multiparameter Models Asymptotics and Connections to Non-Bayesian ApproachesHierarchical ModelsFUNDAMENTALS OF BAYESIAN DATA ANALYSISModel Checking Evaluating, Comparing, and Expanding ModelsModeling Accounting for Data Collection Decision AnalysisADVANCED COMPUTATION Introduction to Bayesian Computation Basics of Markov Chain Simulation Computationally Efficient Markov Chain Simulation Modal and Distributional ApproximationsREGRESSION MODELS Introduction to Regression Models Hierarchical Linear
Yuan, Ying; MacKinnon, David P.
2009-01-01
This article proposes Bayesian analysis of mediation effects. Compared to conventional frequentist mediation analysis, the Bayesian approach has several advantages. First, it allows researchers to incorporate prior information into the mediation analysis, thus potentially improving the efficiency of estimates. Second, under the Bayesian mediation analysis, inference is straightforward and exact, which makes it appealing for studies with small samples. Third, the Bayesian approach is conceptua...
Bayesian Games with Intentions
Bjorndahl, Adam; Halpern, Joseph Y.; Pass, Rafael
2016-01-01
We show that standard Bayesian games cannot represent the full spectrum of belief-dependent preferences. However, by introducing a fundamental distinction between intended and actual strategies, we remove this limitation. We define Bayesian games with intentions, generalizing both Bayesian games and psychological games, and prove that Nash equilibria in psychological games correspond to a special class of equilibria as defined in our setting.
Sour, Angélique; Jenni, Sébastien; Ortí-Suárez, Ana; Schmitt, Julie; Heitz, Valérie; Bolze, Frédéric; Loureiro de Sousa, Paulo; Po, Chrystelle; Bonnet, Célia S; Pallier, Agnès; Tóth, Éva; Ventura, Barbara
2016-05-01
A molecular theranostic agent for magnetic resonance imaging (MRI) and photodynamic therapy (PDT) consisting of four [GdDTTA](-) complexes (DTTA(4-) = diethylenetriamine-N,N,N″,N″-tetraacetate) linked to a meso-tetraphenylporphyrin core, as well as its yttrium(III) analogue, was synthesized. A variety of physicochemical methods were used to characterize the gadolinium(III) conjugate 1 both as an MRI contrast agent and as a photosensitizer. The proton relaxivity measured in H2O at 20 MHz and 25 °C, r1 = 43.7 mmol(-1) s(-1) per gadolinium center, is the highest reported for a bishydrated gadolinium(III)-based contrast agent of medium size and can be related to the rigidity of the molecule. The complex displays also a remarkable singlet oxygen quantum yield of ϕΔ = 0.45 in H2O, similar to that of a meso-tetrasulfonated porphyrin. We also evidenced the ability of the gadolinium(III) conjugate to penetrate in cancer cells with low cytotoxicity. Its phototoxicity on Hela cells was evaluated following incubation at low micromolar concentration and moderate light irradiation (21 J cm(-2)) induced 50% of cell death. Altogether, these results demonstrate the high potential of this conjugate as a theranostic agent for MRI and PDT. PMID:27074089
Characteristic imsets for learning Bayesian network structure
Hemmecke, R.; Lindner, S.; Studený, Milan
2012-01-01
Roč. 53, č. 9 (2012), s. 1336-1349. ISSN 0888-613X R&D Projects: GA MŠk(CZ) 1M0572; GA ČR GA201/08/0539 Institutional support: RVO:67985556 Keywords : learning Bayesian network structure * essential graph * standard imset * characteristic imset * LP relaxation of a polytope Subject RIV: BA - General Mathematics Impact factor: 1.729, year: 2012 http://library.utia.cas.cz/separaty/2012/MTR/studeny-0382596.pdf
Andrade, Tomas
2014-01-01
Momentum relaxation can be built into many holographic models without sacrificing homogeneity of the bulk solution. In this paper we study two such models: one in which translational invariance is broken in the dual theory by spatially-dependent sources for massless scalar fields and another that features an additional neutral scalar field. We turn on a charged scalar field in order to explore the condensation of a charged scalar operator in the dual theories. After demonstrating that the relaxed superconductors we construct are thermodynamically relevant, we find that the finite DC electrical conductivity of the normal phase is replaced by a superfluid pole in the broken phase. Moreover, when the normal phase possesses a Drude behaviour at low frequencies, the optical conductivity of the broken phase at low frequencies can be described by a two-fluid model that is a sum of a Drude peak and a superfluid pole, as was found recently for inhomogeneous holographic superconductors. We also study cases in which thi...
BEAST: Bayesian evolutionary analysis by sampling trees
Drummond Alexei J; Rambaut Andrew
2007-01-01
Abstract Background The evolutionary analysis of molecular sequence variation is a statistical enterprise. This is reflected in the increased use of probabilistic models for phylogenetic inference, multiple sequence alignment, and molecular population genetics. Here we present BEAST: a fast, flexible software architecture for Bayesian analysis of molecular sequences related by an evolutionary tree. A large number of popular stochastic models of sequence evolution are provided and tree-based m...
BEAST: Bayesian evolutionary analysis by sampling trees
Drummond, Alexei J.; Rambaut, Andrew
2007-01-01
Background: The evolutionary analysis of molecular sequence variation is a statistical enterprise. This is reflected in the increased use of probabilistic models for phylogenetic inference, multiple sequence alignment, and molecular population genetics. Here we present BEAST: a fast, flexible software architecture for Bayesian analysis of molecular sequences related by an evolutionary tree. A large number of popular stochastic models of sequence evolution are provided and tree-based models su...
Rubin, Donald B.
1981-01-01
The Bayesian bootstrap is the Bayesian analogue of the bootstrap. Instead of simulating the sampling distribution of a statistic estimating a parameter, the Bayesian bootstrap simulates the posterior distribution of the parameter; operationally and inferentially the methods are quite similar. Because both methods of drawing inferences are based on somewhat peculiar model assumptions and the resulting inferences are generally sensitive to these assumptions, neither method should be applied wit...
Bayesian statistics an introduction
Lee, Peter M
2012-01-01
Bayesian Statistics is the school of thought that combines prior beliefs with the likelihood of a hypothesis to arrive at posterior beliefs. The first edition of Peter Lee’s book appeared in 1989, but the subject has moved ever onwards, with increasing emphasis on Monte Carlo based techniques. This new fourth edition looks at recent techniques such as variational methods, Bayesian importance sampling, approximate Bayesian computation and Reversible Jump Markov Chain Monte Carlo (RJMCMC), providing a concise account of the way in which the Bayesian approach to statistics develops as wel
Understanding Computational Bayesian Statistics
Bolstad, William M
2011-01-01
A hands-on introduction to computational statistics from a Bayesian point of view Providing a solid grounding in statistics while uniquely covering the topics from a Bayesian perspective, Understanding Computational Bayesian Statistics successfully guides readers through this new, cutting-edge approach. With its hands-on treatment of the topic, the book shows how samples can be drawn from the posterior distribution when the formula giving its shape is all that is known, and how Bayesian inferences can be based on these samples from the posterior. These ideas are illustrated on common statistic
Latanowicz, L.; Medycki, W.; Jakubas, R.
2011-08-01
Molecular dynamics of a polycrystalline sample of (CH 3NH 3) 5Bi 2Br 11 (MAPBB) is studied on the basis of the proton T1 (55.2 MHz) relaxation time and the proton second moment of NMR line. The T1 (55.2 MHz) was measured for temperatures from 20 K to 330 K, while the second moment M2 for those from 40 K to 330 K. The proton spin pairs of the methyl and ammonium groups perform a complex stochastic motion being a resultant of four components characterised by the correlation times τ3T, τ3H, τ2, and τ iso, referring to the tunnelling and over the barrier jumps in a triple potential, jumps between two equilibrium sites and isotropic rotation. The theoretical expressions for the spectral densities in the cases of the complex motion considered were derived. For τ3H, τ2, and τ iso the Arrhenius temperature dependence was assumed, while for τ3T - the Schrödinger one. The correlation times τ3H for CH 3 and NH 3 groups differ, which indicates the uncorrelated motion of these groups. The stochastic tunnelling jumps are not present above the temperature T tun at which the thermal energy is higher than the activation energy of jumps over the barrier attributed to the hindered rotation of the CH 3 and NH 3 groups. The T tun temperature is 54.6 K for NH 3 group and 46.5 K for CH 3 group in MAPBB crystal. The tunnelling jumps of the methyl and ammonium protons are responsible for the flattening of T1 temperature dependence at low temperatures. The isotropic tumbling is detectable only from the M2 temperature dependence. The isotropic tumbling reduces the second moment to 4 G2 which is the value of the intermolecular part of the second moment. The motion characterised by the correlation time τ2 is well detectable from both T1 and M2 temperature dependences. This motion causes the appearance of T1 minimum at 130 K and reduction of the second moment to the 7.7 G2 value. The small tunnelling splitting ω T of the same value for the methyl and ammonium groups was estimated as
Frühwirth-Schnatter, Sylvia
1990-01-01
In the paper at hand we apply it to Bayesian statistics to obtain "Fuzzy Bayesian Inference". In the subsequent sections we will discuss a fuzzy valued likelihood function, Bayes' theorem for both fuzzy data and fuzzy priors, a fuzzy Bayes' estimator, fuzzy predictive densities and distributions, and fuzzy H.P.D .-Regions. (author's abstract)
Yuan, Ying; MacKinnon, David P.
2009-01-01
In this article, we propose Bayesian analysis of mediation effects. Compared with conventional frequentist mediation analysis, the Bayesian approach has several advantages. First, it allows researchers to incorporate prior information into the mediation analysis, thus potentially improving the efficiency of estimates. Second, under the Bayesian…
Nima Kasraie
2011-01-01
Full Text Available The aims of this study were to determine whether standard extracellular contrast agents of Gd(III ions in combination with a polymeric entity susceptible to hydrolytic degradation over a finite period of time, such as Hyaluronic Acid (HA, have sufficient vascular residence time to obtain comparable vascular imaging to current conventional compounds and to obtain sufficient data to show proof of concept that HA with Gd-DTPA ligands could be useful as vascular imaging agents. We assessed the dynamic relaxivity of the HA bound DTPA compounds using a custom-made phantom, as well as relaxation rates at 10.72 MHz with concentrations ranging between 0.09 and 7.96 mM in phosphate-buffered saline. Linear dependences of static longitudinal relaxation rate (R1 on concentration were found for most measured samples, and the HA samples continued to produce high signal strength after 24 hours after injection into a dialysis cassette at 3T, showing superior dynamic relaxivity values compared to conventional contrast media such as Gd-DTPA-BMA.
The aims of this study were to determine whether standard extracellular contrast agents of Gd(III) ions in combination with a polymeric entity susceptible to hydrolytic degradation over a finite period of time, such as Hyaluronic Acid (HA), have sufficient vascular residence time to obtain comparable vascular imaging to current conventional compounds and to obtain sufficient data to show proof of concept that HA with Gd-DTPA ligands could be useful as vascular imaging agents. We assessed the dynamic relaxivity of the HA bound DTPA compounds using a custom-made phantom, as well as relaxation rates at 10.72 MHz with concentrations ranging between 0.09 and 7.96 mM in phosphate-buffered saline. Linear dependences of static longitudinal relaxation rate (R1) on concentration were found for most measured samples, and the HA samples continued to produce high signal strength after 24 hours after injection into a dialysis cassette at 3T, showing superior dynamic relaxivity values compared to conventional contrast media such as Gd-DTPA-BMA
Non-monotonic behaviour in relaxation dynamics of image restoration
We have investigated the relaxation dynamics of image restoration through a Bayesian approach. The relaxation dynamics is much faster at zero temperature than at the Nishimori temperature where the pixel-wise error rate is minimized in equilibrium. At low temperature, we observed non-monotonic development of the overlap. We suggest that the optimal performance is realized through premature termination in the relaxation processes in the case of the infinite-range model. We also performed Markov chain Monte Carlo simulations to clarify the underlying mechanism of non-trivial behaviour at low temperature by checking the local field distributions of each pixel
Structure-based bayesian sparse reconstruction
Quadeer, Ahmed Abdul
2012-12-01
Sparse signal reconstruction algorithms have attracted research attention due to their wide applications in various fields. In this paper, we present a simple Bayesian approach that utilizes the sparsity constraint and a priori statistical information (Gaussian or otherwise) to obtain near optimal estimates. In addition, we make use of the rich structure of the sensing matrix encountered in many signal processing applications to develop a fast sparse recovery algorithm. The computational complexity of the proposed algorithm is very low compared with the widely used convex relaxation methods as well as greedy matching pursuit techniques, especially at high sparsity. © 1991-2012 IEEE.
Baldo, M.; Grassi, A.; Guidoni, L.; Nicolini, M.; Pappalardo, G. C.; Viti, V.
The spin-lattice relaxation times ( T1) of carbon-13 resonances of the drug 2-oxopyrrolidin- 1-ylacetamide ( 2OPYAC) were determined in CDCl 3 + DMSO and H 2O solutions to investigate the internal conformational flexibility. The measured T1s for the hydrogen-bearing carbon atoms of the 2-pyrrolidone ring fragment were diagnostic of a rigid conformation with respect to the acetamide linked moiety. The model of anisotropic reorientation of a rigid body was used to analyse the measured relaxation data in terms of a single conformation. Owing to the small number of T1 data available the fitting procedure for each of the possible conformations failed. The structure corresponding to the rigid conformation was therefore considered to be the one that is strongly stabilized by internal hydrogen bonding as predicted on the basis of theoretical MO ab initio quantum chemical calculations.
Granade, Christopher; Cory, D G
2015-01-01
In recent years, Bayesian methods have been proposed as a solution to a wide range of issues in quantum state and process tomography. State-of- the-art Bayesian tomography solutions suffer from three problems: numerical intractability, a lack of informative prior distributions, and an inability to track time-dependent processes. Here, we solve all three problems. First, we use modern statistical methods, as pioneered by Husz\\'ar and Houlsby and by Ferrie, to make Bayesian tomography numerically tractable. Our approach allows for practical computation of Bayesian point and region estimators for quantum states and channels. Second, we propose the first informative priors on quantum states and channels. Finally, we develop a method that allows online tracking of time-dependent states and estimates the drift and diffusion processes affecting a state. We provide source code and animated visual examples for our methods.
Bayesian exploratory factor analysis
Gabriella Conti; Sylvia Frühwirth-Schnatter; James Heckman; Rémi Piatek
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on ad hoc classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the corresponding factor loadings. Classical identifi cation criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo study c...
Bayesian Exploratory Factor Analysis
Conti, Gabriella; Frühwirth-Schnatter, Sylvia; Heckman, James J.; Piatek, Rémi
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on ad hoc classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the corresponding factor loadings. Classical identification criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo study co...
Bayesian Exploratory Factor Analysis
Gabriella Conti; Sylvia Fruehwirth-Schnatter; Heckman, James J.; Remi Piatek
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on \\emph{ad hoc} classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the corresponding factor loadings. Classical identification criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo s...
Bayesian exploratory factor analysis
Conti, Gabriella; Frühwirth-Schnatter, Sylvia; Heckman, James J.; Piatek, Rémi
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on ad hoc classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the corresponding factor loadings. Classical identification criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo st...
Bayesian exploratory factor analysis
Conti, Gabriella; Frühwirth-Schnatter, Sylvia; Heckman, James; Piatek, Rémi
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on ad hoc classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the corresponding factor loadings. Classical identification criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo study co...
Carbonetto, Peter; Kisynski, Jacek; De Freitas, Nando; Poole, David L
2012-01-01
The Bayesian Logic (BLOG) language was recently developed for defining first-order probability models over worlds with unknown numbers of objects. It handles important problems in AI, including data association and population estimation. This paper extends BLOG by adopting generative processes over function spaces - known as nonparametrics in the Bayesian literature. We introduce syntax for reasoning about arbitrary collections of objects, and their properties, in an intuitive manner. By expl...
Bayesian default probability models
Andrlíková, Petra
2014-01-01
This paper proposes a methodology for default probability estimation for low default portfolios, where the statistical inference may become troublesome. The author suggests using logistic regression models with the Bayesian estimation of parameters. The piecewise logistic regression model and Box-Cox transformation of credit risk score is used to derive the estimates of probability of default, which extends the work by Neagu et al. (2009). The paper shows that the Bayesian models are more acc...
Bayesian phylogeography finds its roots.
Philippe Lemey
2009-09-01
Full Text Available As a key factor in endemic and epidemic dynamics, the geographical distribution of viruses has been frequently interpreted in the light of their genetic histories. Unfortunately, inference of historical dispersal or migration patterns of viruses has mainly been restricted to model-free heuristic approaches that provide little insight into the temporal setting of the spatial dynamics. The introduction of probabilistic models of evolution, however, offers unique opportunities to engage in this statistical endeavor. Here we introduce a Bayesian framework for inference, visualization and hypothesis testing of phylogeographic history. By implementing character mapping in a Bayesian software that samples time-scaled phylogenies, we enable the reconstruction of timed viral dispersal patterns while accommodating phylogenetic uncertainty. Standard Markov model inference is extended with a stochastic search variable selection procedure that identifies the parsimonious descriptions of the diffusion process. In addition, we propose priors that can incorporate geographical sampling distributions or characterize alternative hypotheses about the spatial dynamics. To visualize the spatial and temporal information, we summarize inferences using virtual globe software. We describe how Bayesian phylogeography compares with previous parsimony analysis in the investigation of the influenza A H5N1 origin and H5N1 epidemiological linkage among sampling localities. Analysis of rabies in West African dog populations reveals how virus diffusion may enable endemic maintenance through continuous epidemic cycles. From these analyses, we conclude that our phylogeographic framework will make an important asset in molecular epidemiology that can be easily generalized to infer biogeogeography from genetic data for many organisms.
... related breathing difficulties. Learn some ways to control breathing and some techniques to help you reach a greater level of relaxation during your day: Diaphragmatic Breathing Minimizing Shortness of Breath Instant Relaxation Drill Meditation ...
Using both quantum and semi-classical methods, we calculate the rates for radiative association and charge transfer in cold collisions of Yb+ with Ca. We demonstrate the fidelity of the local optical potential method in predictions for the total radiative relaxation rates. We find a large variation in the isotope dependence of the cross sections at ultra-cold gas temperatures. However, at cold temperatures, 1 mK −15 cm3 s−1. It is about five orders of magnitude smaller than the chemical reaction rate measured in Rellergert et al (2011 Phys. Rev. Lett. 107 243201). (paper)
Bayesian ensemble refinement by replica simulations and reweighting
Hummer, Gerhard
2015-01-01
We describe different Bayesian ensemble refinement methods, examine their interrelation, and discuss their practical application. With ensemble refinement, the properties of dynamic and partially disordered (bio)molecular structures can be characterized by integrating a wide range of experimental data, including measurements of ensemble-averaged observables. We start from a Bayesian formulation in which the posterior is a functional that ranks different configuration space distributions. By maximizing this posterior, we derive an optimal Bayesian ensemble distribution. For discrete configurations, this optimal distribution is identical to that obtained by the maximum entropy "ensemble refinement of SAXS" (EROS) formulation. Bayesian replica ensemble refinement enhances the sampling of relevant configurations by imposing restraints on averages of observables in coupled replica molecular dynamics simulations. We find that the strength of the restraint scales with the number of replicas and we show that this sca...
Approximate Bayesian Computation in Large Scale Structure: constraining the galaxy-halo connection
Hahn, ChangHoon; Vakili, Mohammadjavad; Walsh, Kilian; Hearin, Andrew P.; Hogg, David W.; Cambpell, Duncan
2016-01-01
The standard approaches to Bayesian parameter inference in large scale structure (LSS) assume a Gaussian functional form (chi-squared form) for the likelihood. They are also typically restricted to measurements such as the two point correlation function. Likelihood free inferences such as Approximate Bayesian Computation (ABC) make inference possible without assuming any functional form for the likelihood, thereby relaxing the assumptions and restrictions of the standard approach. Instead it ...
Stress relaxation of bi-disperse polystyrene melts
Hengeller, Ludovica; Huang, Qian; Dorokhin, Andriy;
2016-01-01
We present start-up of uniaxial extension followed by stress relaxation experiments of a bi-disperse 50 % by weight blend of 95k and 545k molecular weight polystyrene. We also show, for comparison, stress relaxation measurements of the polystyrene melts with molecular weight 95k and 545k, which are...
Bayesian least squares deconvolution
Asensio Ramos, A.; Petit, P.
2015-11-01
Aims: We develop a fully Bayesian least squares deconvolution (LSD) that can be applied to the reliable detection of magnetic signals in noise-limited stellar spectropolarimetric observations using multiline techniques. Methods: We consider LSD under the Bayesian framework and we introduce a flexible Gaussian process (GP) prior for the LSD profile. This prior allows the result to automatically adapt to the presence of signal. We exploit several linear algebra identities to accelerate the calculations. The final algorithm can deal with thousands of spectral lines in a few seconds. Results: We demonstrate the reliability of the method with synthetic experiments and we apply it to real spectropolarimetric observations of magnetic stars. We are able to recover the magnetic signals using a small number of spectral lines, together with the uncertainty at each velocity bin. This allows the user to consider if the detected signal is reliable. The code to compute the Bayesian LSD profile is freely available.
Bayesian least squares deconvolution
Ramos, A Asensio
2015-01-01
Aims. To develop a fully Bayesian least squares deconvolution (LSD) that can be applied to the reliable detection of magnetic signals in noise-limited stellar spectropolarimetric observations using multiline techniques. Methods. We consider LSD under the Bayesian framework and we introduce a flexible Gaussian Process (GP) prior for the LSD profile. This prior allows the result to automatically adapt to the presence of signal. We exploit several linear algebra identities to accelerate the calculations. The final algorithm can deal with thousands of spectral lines in a few seconds. Results. We demonstrate the reliability of the method with synthetic experiments and we apply it to real spectropolarimetric observations of magnetic stars. We are able to recover the magnetic signals using a small number of spectral lines, together with the uncertainty at each velocity bin. This allows the user to consider if the detected signal is reliable. The code to compute the Bayesian LSD profile is freely available.
Loredo, T J
2004-01-01
I describe a framework for adaptive scientific exploration based on iterating an Observation--Inference--Design cycle that allows adjustment of hypotheses and observing protocols in response to the results of observation on-the-fly, as data are gathered. The framework uses a unified Bayesian methodology for the inference and design stages: Bayesian inference to quantify what we have learned from the available data and predict future data, and Bayesian decision theory to identify which new observations would teach us the most. When the goal of the experiment is simply to make inferences, the framework identifies a computationally efficient iterative ``maximum entropy sampling'' strategy as the optimal strategy in settings where the noise statistics are independent of signal properties. Results of applying the method to two ``toy'' problems with simulated data--measuring the orbit of an extrasolar planet, and locating a hidden one-dimensional object--show the approach can significantly improve observational eff...
Bayesian and frequentist inequality tests
David M. Kaplan; Zhuo, Longhao
2016-01-01
Bayesian and frequentist criteria are fundamentally different, but often posterior and sampling distributions are asymptotically equivalent (and normal). We compare Bayesian and frequentist hypothesis tests of inequality restrictions in such cases. For finite-dimensional parameters, if the null hypothesis is that the parameter vector lies in a certain half-space, then the Bayesian test has (frequentist) size $\\alpha$; if the null hypothesis is any other convex subspace, then the Bayesian test...
Protein dynamics from nuclear magnetic relaxation.
Charlier, Cyril; Cousin, Samuel F; Ferrage, Fabien
2016-05-01
Nuclear magnetic resonance is a ubiquitous spectroscopic tool to explore molecules with atomic resolution. Nuclear magnetic relaxation is intimately connected to molecular motions. Many methods and models have been developed to measure and interpret the characteristic rates of nuclear magnetic relaxation in proteins. These approaches shed light on a rich and diverse range of motions covering timescales from picoseconds to seconds. Here, we introduce some of the basic concepts upon which these approaches are built and provide a series of illustrations. PMID:26932314
Relaxation processes in mixed gas dynamic lasers
Soloukhin, R.I.; Fomin, N.A.
1978-12-01
With the solution of gasdynamic and CO/sub 2/--N/sub 2/ vibrational relaxation equations, analysis was made of vibrational energy losses associated with relaxation processes in an inverted molecular system with selective thermal excitation and supersonic flow mixing of the pumping and radiative gas components. Optimum operation conditions were determined, and a possibility of regimes with low vibrational losses was found to be feasible at available specific energies up to 200 J/g.
Toshiro SHIBANO; Paul M VANHOUTTE
2003-01-01
AIM: To determine whether or not low molecular G-proteins are involved in the endothelium-dependent relaxations to bradykinin. METHODS: The effects of botulinum ADP-ribosyltranferase C3 were studied in porcine coronary arteries and endothelial cells. RESULTS: Incubation of membrane fractions isolated from endothelial cells with the enzyme and 32p-NAD resulted in the ribosylation of the proteins with molecular weight of 24-25 kDa. Radio labelling of these proteins was suppressed in the presence of guanosine 5t-O-(3-thiotriphosphate) (GTP-yS), a hydrolysis-resistant analog of GTP. In the isolated arteries, ADP-ribosyltransferase C3 attenuated the relaxations tobradykinin during contractions with prostaglandin F2α in the presence of tween 80 (non ionic detergent), but not in the absence of tween 80. CONCLUSION: Low molecular weight G-proteins of the Rho family contribute to the mechanism of relaxation induced by bradykinin.
Bayesian multiple target tracking
Streit, Roy L
2013-01-01
This second edition has undergone substantial revision from the 1999 first edition, recognizing that a lot has changed in the multiple target tracking field. One of the most dramatic changes is in the widespread use of particle filters to implement nonlinear, non-Gaussian Bayesian trackers. This book views multiple target tracking as a Bayesian inference problem. Within this framework it develops the theory of single target tracking, multiple target tracking, and likelihood ratio detection and tracking. In addition to providing a detailed description of a basic particle filter that implements
Bayesian Exploratory Factor Analysis
Conti, Gabriella; Frühwirth-Schnatter, Sylvia; Heckman, James J.;
2014-01-01
This paper develops and applies a Bayesian approach to Exploratory Factor Analysis that improves on ad hoc classical approaches. Our framework relies on dedicated factor models and simultaneously determines the number of factors, the allocation of each measurement to a unique factor, and the...... corresponding factor loadings. Classical identification criteria are applied and integrated into our Bayesian procedure to generate models that are stable and clearly interpretable. A Monte Carlo study confirms the validity of the approach. The method is used to produce interpretable low dimensional aggregates...
Wang, Wei; Zhou, Qian; Dong, Yuan; Yeo, Yee-Chia, E-mail: yeo@ieee.org [Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117576 (Singapore); Tok, Eng Soon [Department of Physics, National University of Singapore, Singapore 117551 (Singapore)
2015-06-08
We investigated the critical thickness (h{sub c}) for plastic relaxation of Ge{sub 1−x}Sn{sub x} grown by molecular beam epitaxy. Ge{sub 1−x}Sn{sub x} films with various Sn mole fraction x (x ≤ 0.17) and different thicknesses were grown on Ge(001). The strain relaxation of Ge{sub 1−x}Sn{sub x} films and the h{sub c} were investigated by high-resolution x-ray diffraction and reciprocal space mapping. It demonstrates that the measured h{sub c} values of Ge{sub 1−x}Sn{sub x} layers are as much as an order of magnitude larger than that predicted by the Matthews and Blakeslee (M-B) model. The People and Bean (P-B) model was also used to predict the h{sub c} values in Ge{sub 1−x}Sn{sub x}/Ge system. The measured h{sub c} values for various Sn content follow the trend, but slightly larger than that predicted by the P-B model.
Bayesian Geostatistical Design
Diggle, Peter; Lophaven, Søren Nymand
2006-01-01
locations to, or deletion of locations from, an existing design, and prospective design, which consists of choosing positions for a new set of sampling locations. We propose a Bayesian design criterion which focuses on the goal of efficient spatial prediction whilst allowing for the fact that model...
Krejsa, Jiří; Věchet, S.
Bratislava: Slovak University of Technology in Bratislava, 2010, s. 217-222. ISBN 978-80-227-3353-3. [Robotics in Education . Bratislava (SK), 16.09.2010-17.09.2010] Institutional research plan: CEZ:AV0Z20760514 Keywords : mobile robot localization * bearing only beacons * Bayesian filters Subject RIV: JD - Computer Applications, Robotics
Antoniou, Constantinos; Harrison, Glenn W.; Lau, Morten I.;
2015-01-01
A large literature suggests that many individuals do not apply Bayes’ Rule when making decisions that depend on them correctly pooling prior information and sample data. We replicate and extend a classic experimental study of Bayesian updating from psychology, employing the methods of experimenta...
Bayesian Independent Component Analysis
Winther, Ole; Petersen, Kaare Brandt
2007-01-01
In this paper we present an empirical Bayesian framework for independent component analysis. The framework provides estimates of the sources, the mixing matrix and the noise parameters, and is flexible with respect to choice of source prior and the number of sources and sensors. Inside the engine...
Noncausal Bayesian Vector Autoregression
Lanne, Markku; Luoto, Jani
We propose a Bayesian inferential procedure for the noncausal vector autoregressive (VAR) model that is capable of capturing nonlinearities and incorporating effects of missing variables. In particular, we devise a fast and reliable posterior simulator that yields the predictive distribution as a...
Loredo, Thomas J.
2004-04-01
I describe a framework for adaptive scientific exploration based on iterating an Observation-Inference-Design cycle that allows adjustment of hypotheses and observing protocols in response to the results of observation on-the-fly, as data are gathered. The framework uses a unified Bayesian methodology for the inference and design stages: Bayesian inference to quantify what we have learned from the available data and predict future data, and Bayesian decision theory to identify which new observations would teach us the most. When the goal of the experiment is simply to make inferences, the framework identifies a computationally efficient iterative ``maximum entropy sampling'' strategy as the optimal strategy in settings where the noise statistics are independent of signal properties. Results of applying the method to two ``toy'' problems with simulated data-measuring the orbit of an extrasolar planet, and locating a hidden one-dimensional object-show the approach can significantly improve observational efficiency in settings that have well-defined nonlinear models. I conclude with a list of open issues that must be addressed to make Bayesian adaptive exploration a practical and reliable tool for optimizing scientific exploration.
Bayesian logistic regression analysis
Van Erp, H.R.N.; Van Gelder, P.H.A.J.M.
2012-01-01
In this paper we present a Bayesian logistic regression analysis. It is found that if one wishes to derive the posterior distribution of the probability of some event, then, together with the traditional Bayes Theorem and the integrating out of nuissance parameters, the Jacobian transformation is an
A model electronic Hamiltonian of [Fe(bpy)3]2+, which was recently refined for use in molecular dynamics simulations, is reviewed with some additional results. In particular, the quality of the refined model Hamiltonian is examined in terms of the vibrational frequencies and solvation structures of the lowest singlet and quintet states
Graphical abstract: Display Omitted - Abstract: Gel electrolyte based on low molecular weight organic gelator methyl-4,6-O-(p-nitrobenzylidene)-α-D-glucopyranoside was formed by the self-assembly phenomena in aqueous solution of high temperature ionic liquid tetramethylammonium bromide. The solidification process was based on sol-gel technique with controlled gelation temperature. When the temperature was below the characteristic gel-sol phase transition temperature, Tgs, the gel electrolyte was solid-like. The gel electrolytes showed enhanced ionic conductivity to those of the pure electrolyte in liquid state in whole temperature range below Tgs. The thermal stability, ionic conductivity and molecular dynamics investigated as a function of temperature and concentration of the gelator, together with the gel microstructure were performed to get some insight in to the origin of the enhanced conductivity properties. Intermolecular interaction between ion complexes and gelator aggregates was implicated by the data obtained and suggested as the origin of the conductivity enhancement effect
Probability and Bayesian statistics
1987-01-01
This book contains selected and refereed contributions to the "Inter national Symposium on Probability and Bayesian Statistics" which was orga nized to celebrate the 80th birthday of Professor Bruno de Finetti at his birthplace Innsbruck in Austria. Since Professor de Finetti died in 1985 the symposium was dedicated to the memory of Bruno de Finetti and took place at Igls near Innsbruck from 23 to 26 September 1986. Some of the pa pers are published especially by the relationship to Bruno de Finetti's scientific work. The evolution of stochastics shows growing importance of probability as coherent assessment of numerical values as degrees of believe in certain events. This is the basis for Bayesian inference in the sense of modern statistics. The contributions in this volume cover a broad spectrum ranging from foundations of probability across psychological aspects of formulating sub jective probability statements, abstract measure theoretical considerations, contributions to theoretical statistics an...
Bayesian Magic in Asteroseismology
Kallinger, T.
2015-09-01
Only a few years ago asteroseismic observations were so rare that scientists had plenty of time to work on individual data sets. They could tune their algorithms in any possible way to squeeze out the last bit of information. Nowadays this is impossible. With missions like MOST, CoRoT, and Kepler we basically drown in new data every day. To handle this in a sufficient way statistical methods become more and more important. This is why Bayesian techniques started their triumph march across asteroseismology. I will go with you on a journey through Bayesian Magic Land, that brings us to the sea of granulation background, the forest of peakbagging, and the stony alley of model comparison.
Bayesian Nonparametric Graph Clustering
Banerjee, Sayantan; Akbani, Rehan; Baladandayuthapani, Veerabhadran
2015-01-01
We present clustering methods for multivariate data exploiting the underlying geometry of the graphical structure between variables. As opposed to standard approaches that assume known graph structures, we first estimate the edge structure of the unknown graph using Bayesian neighborhood selection approaches, wherein we account for the uncertainty of graphical structure learning through model-averaged estimates of the suitable parameters. Subsequently, we develop a nonparametric graph cluster...
Approximate Bayesian recursive estimation
Kárný, Miroslav
2014-01-01
Roč. 285, č. 1 (2014), s. 100-111. ISSN 0020-0255 R&D Projects: GA ČR GA13-13502S Institutional support: RVO:67985556 Keywords : Approximate parameter estimation * Bayesian recursive estimation * Kullback–Leibler divergence * Forgetting Subject RIV: BB - Applied Statistics, Operational Research Impact factor: 4.038, year: 2014 http://library.utia.cas.cz/separaty/2014/AS/karny-0425539.pdf
Bayesian Benchmark Dose Analysis
Fang, Qijun; Piegorsch, Walter W.; Barnes, Katherine Y.
2014-01-01
An important objective in environmental risk assessment is estimation of minimum exposure levels, called Benchmark Doses (BMDs) that induce a pre-specified Benchmark Response (BMR) in a target population. Established inferential approaches for BMD analysis typically involve one-sided, frequentist confidence limits, leading in practice to what are called Benchmark Dose Lower Limits (BMDLs). Appeal to Bayesian modeling and credible limits for building BMDLs is far less developed, however. Indee...
Bayesian Generalized Rating Curves
Helgi Sigurðarson 1985
2014-01-01
A rating curve is a curve or a model that describes the relationship between water elevation, or stage, and discharge in an observation site in a river. The rating curve is fit from paired observations of stage and discharge. The rating curve then predicts discharge given observations of stage and this methodology is applied as stage is substantially easier to directly observe than discharge. In this thesis a statistical rating curve model is proposed working within the framework of Bayesian...
Heteroscedastic Treed Bayesian Optimisation
Assael, John-Alexander M.; Wang, Ziyu; Shahriari, Bobak; De Freitas, Nando
2014-01-01
Optimising black-box functions is important in many disciplines, such as tuning machine learning models, robotics, finance and mining exploration. Bayesian optimisation is a state-of-the-art technique for the global optimisation of black-box functions which are expensive to evaluate. At the core of this approach is a Gaussian process prior that captures our belief about the distribution over functions. However, in many cases a single Gaussian process is not flexible enough to capture non-stat...
Efficient Bayesian Phase Estimation
Wiebe, Nathan; Granade, Chris
2016-07-01
We introduce a new method called rejection filtering that we use to perform adaptive Bayesian phase estimation. Our approach has several advantages: it is classically efficient, easy to implement, achieves Heisenberg limited scaling, resists depolarizing noise, tracks time-dependent eigenstates, recovers from failures, and can be run on a field programmable gate array. It also outperforms existing iterative phase estimation algorithms such as Kitaev's method.
Brody, Samuel; Lapata, Mirella
2009-01-01
Sense induction seeks to automatically identify word senses directly from a corpus. A key assumption underlying previous work is that the context surrounding an ambiguous word is indicative of its meaning. Sense induction is thus typically viewed as an unsupervised clustering problem where the aim is to partition a word’s contexts into different classes, each representing a word sense. Our work places sense induction in a Bayesian context by modeling the contexts of the ambiguous word as samp...
Bayesian Neural Word Embedding
Barkan, Oren
2016-01-01
Recently, several works in the domain of natural language processing presented successful methods for word embedding. Among them, the Skip-gram (SG) with negative sampling, known also as Word2Vec, advanced the state-of-the-art of various linguistics tasks. In this paper, we propose a scalable Bayesian neural word embedding algorithm that can be beneficial to general item similarity tasks as well. The algorithm relies on a Variational Bayes solution for the SG objective and a detailed step by ...
Wiegerinck, Wim; Schoenaker, Christiaan; Duane, Gregory
2016-04-01
Recently, methods for model fusion by dynamically combining model components in an interactive ensemble have been proposed. In these proposals, fusion parameters have to be learned from data. One can view these systems as parametrized dynamical systems. We address the question of learnability of dynamical systems with respect to both short term (vector field) and long term (attractor) behavior. In particular we are interested in learning in the imperfect model class setting, in which the ground truth has a higher complexity than the models, e.g. due to unresolved scales. We take a Bayesian point of view and we define a joint log-likelihood that consists of two terms, one is the vector field error and the other is the attractor error, for which we take the L1 distance between the stationary distributions of the model and the assumed ground truth. In the context of linear models (like so-called weighted supermodels), and assuming a Gaussian error model in the vector fields, vector field learning leads to a tractable Gaussian solution. This solution can then be used as a prior for the next step, Bayesian attractor learning, in which the attractor error is used as a log-likelihood term. Bayesian attractor learning is implemented by elliptical slice sampling, a sampling method for systems with a Gaussian prior and a non Gaussian likelihood. Simulations with a partially observed driven Lorenz 63 system illustrate the approach.
Bayesian theory and applications
Dellaportas, Petros; Polson, Nicholas G; Stephens, David A
2013-01-01
The development of hierarchical models and Markov chain Monte Carlo (MCMC) techniques forms one of the most profound advances in Bayesian analysis since the 1970s and provides the basis for advances in virtually all areas of applied and theoretical Bayesian statistics. This volume guides the reader along a statistical journey that begins with the basic structure of Bayesian theory, and then provides details on most of the past and present advances in this field. The book has a unique format. There is an explanatory chapter devoted to each conceptual advance followed by journal-style chapters that provide applications or further advances on the concept. Thus, the volume is both a textbook and a compendium of papers covering a vast range of topics. It is appropriate for a well-informed novice interested in understanding the basic approach, methods and recent applications. Because of its advanced chapters and recent work, it is also appropriate for a more mature reader interested in recent applications and devel...
How does the relaxation of a supercooled liquid depend on its microscopic dynamics?
Gleim, Tobias; Kob, Walter; Binder, Kurt
1998-01-01
Using molecular dynamics computer simulations we investigate how the relaxation dynamics of a simple supercooled liquid with Newtonian dynamics differs from the one with a stochastic dynamics. We find that, apart from the early beta-relaxation regime, the two dynamics give rise to the same relaxation behavior. The increase of the relaxation times of the system upon cooling, the details of the alpha-relaxation, as well as the wave vector dependence of the Edwards-Anderson-parameters are indepe...
Unbounded Bayesian Optimization via Regularization
Shahriari, Bobak; Bouchard-Côté, Alexandre; De Freitas, Nando
2015-01-01
Bayesian optimization has recently emerged as a popular and efficient tool for global optimization and hyperparameter tuning. Currently, the established Bayesian optimization practice requires a user-defined bounding box which is assumed to contain the optimizer. However, when little is known about the probed objective function, it can be difficult to prescribe such bounds. In this work we modify the standard Bayesian optimization framework in a principled way to allow automatic resizing of t...
Bayesian optimization for materials design
Frazier, Peter I.; Wang, Jialei
2015-01-01
We introduce Bayesian optimization, a technique developed for optimizing time-consuming engineering simulations and for fitting machine learning models on large datasets. Bayesian optimization guides the choice of experiments during materials design and discovery to find good material designs in as few experiments as possible. We focus on the case when materials designs are parameterized by a low-dimensional vector. Bayesian optimization is built on a statistical technique called Gaussian pro...
Charge relaxation dynamics of an electrolytic nanocapacitor
Thakore, Vaibhav
2013-01-01
Understanding ion relaxation dynamics in overlapping electric double layers (EDLs) is critical for the development of efficient nanotechnology based electrochemical energy storage, electrochemomechanical energy conversion and bioelectrochemical sensing devices besides controlled synthesis of nanostructured materials. Here, using Lattice Boltzmann (LB) method, we present results from the simulations of an electrolytic nanocapacitor subjected to a step potential at t = 0 for various degrees of EDL overlap, solvent viscosities, ratios of cation to anion diffusivity and electrode separations. A continuously varying molecular speed dependent relaxation time, proposed for use with the LB equation, recovers the correct microscopic description of molecular collision phenomena and holds promise for enhancing the stability of the LB algorithm. Results for large EDL overlap showed oscillatory behavior for ionic current densities in contrast to monotonic relaxation to equilibrium for low EDL overlap. Further, at low solv...
The experimental and theoretical two-dimensional nuclear Overhauser effect spectra, double-quantum-filtered COSY experiments, and molecular mechanics calculations on the self-complementary decamer [d-(5'ATATATATAT3')]2 presented here indicate that the duplex as a time-average assumes a wrinkled D conformation (B DNA family) with a hydration tunnel in the minor groove. Formation of the tunnel is favored by non-bonded and electrostatic interchain sugar-phosphate and ion-DNA interactions in the minor groove. The size of the tunnel in the DNA perfectly accomodates three types of water molecules - one bridging interstrand N3 atoms of adenine, another water molecule bridging interstrand O2 atoms of thymine bases and another water molecule bridging the above mentioned two water molecules. 31 refs.; 3 figs.; 2 tabs
Relaxation Techniques for Health
... hasn't been shown to relieve labor pain. Depression An evaluation of 15 studies concluded that relaxation ... links Twitter Read our disclaimer about external links Facebook Read our disclaimer about external links YouTube Read ...
Perturbations and quantum relaxation
Kandhadai, Adithya
2016-01-01
We investigate whether small perturbations can cause relaxation to quantum equilibrium over very long timescales. We consider in particular a two-dimensional harmonic oscillator, which can serve as a model of a field mode on expanding space. We assume an initial wave function with small perturbations to the ground state. We present evidence that the trajectories are highly confined so as to preclude relaxation to equilibrium even over very long timescales. Cosmological implications are briefly discussed.
Sarwate, Anand D.; Gastpar, Michael
2012-01-01
The arbitrarily varying channel (AVC) is a conservative way of modeling an unknown interference, and the corresponding capacity results are pessimistic. We reconsider the Gaussian AVC by relaxing the classical model and thereby weakening the adversarial nature of the interference. We examine three different relaxations. First, we show how a very small amount of common randomness between transmitter and receiver is sufficient to achieve the rates of fully randomized codes. Second, akin to the ...
Bayesian nonparametric data analysis
Müller, Peter; Jara, Alejandro; Hanson, Tim
2015-01-01
This book reviews nonparametric Bayesian methods and models that have proven useful in the context of data analysis. Rather than providing an encyclopedic review of probability models, the book’s structure follows a data analysis perspective. As such, the chapters are organized by traditional data analysis problems. In selecting specific nonparametric models, simpler and more traditional models are favored over specialized ones. The discussed methods are illustrated with a wealth of examples, including applications ranging from stylized examples to case studies from recent literature. The book also includes an extensive discussion of computational methods and details on their implementation. R code for many examples is included in on-line software pages.
Decentralized Distributed Bayesian Estimation
Dedecius, Kamil; Sečkárová, Vladimíra
Praha: ÚTIA AVČR, v.v.i, 2011 - (Janžura, M.; Ivánek, J.). s. 16-16 [7th International Workshop on Data–Algorithms–Decision Making. 27.11.2011-29.11.2011, Mariánská] R&D Projects: GA ČR 102/08/0567; GA ČR GA102/08/0567 Institutional research plan: CEZ:AV0Z10750506 Keywords : estimation * distributed estimation * model Subject RIV: BB - Applied Statistics, Operational Research http://library.utia.cas.cz/separaty/2011/AS/dedecius-decentralized distributed bayesian estimation.pdf
Congdon, Peter
2014-01-01
This book provides an accessible approach to Bayesian computing and data analysis, with an emphasis on the interpretation of real data sets. Following in the tradition of the successful first edition, this book aims to make a wide range of statistical modeling applications accessible using tested code that can be readily adapted to the reader's own applications. The second edition has been thoroughly reworked and updated to take account of advances in the field. A new set of worked examples is included. The novel aspect of the first edition was the coverage of statistical modeling using WinBU
Computationally efficient Bayesian tracking
Aughenbaugh, Jason; La Cour, Brian
2012-06-01
In this paper, we describe the progress we have achieved in developing a computationally efficient, grid-based Bayesian fusion tracking system. In our approach, the probability surface is represented by a collection of multidimensional polynomials, each computed adaptively on a grid of cells representing state space. Time evolution is performed using a hybrid particle/grid approach and knowledge of the grid structure, while sensor updates use a measurement-based sampling method with a Delaunay triangulation. We present an application of this system to the problem of tracking a submarine target using a field of active and passive sonar buoys.
Improved iterative Bayesian unfolding
D'Agostini, G
2010-01-01
This paper reviews the basic ideas behind a Bayesian unfolding published some years ago and improves their implementation. In particular, uncertainties are now treated at all levels by probability density functions and their propagation is performed by Monte Carlo integration. Thus, small numbers are better handled and the final uncertainty does not rely on the assumption of normality. Theoretical and practical issues concerning the iterative use of the algorithm are also discussed. The new program, implemented in the R language, is freely available, together with sample scripts to play with toy models.
Bayesian Inference on Gravitational Waves
Asad Ali
2015-12-01
Full Text Available The Bayesian approach is increasingly becoming popular among the astrophysics data analysis communities. However, the Pakistan statistics communities are unaware of this fertile interaction between the two disciplines. Bayesian methods have been in use to address astronomical problems since the very birth of the Bayes probability in eighteenth century. Today the Bayesian methods for the detection and parameter estimation of gravitational waves have solid theoretical grounds with a strong promise for the realistic applications. This article aims to introduce the Pakistan statistics communities to the applications of Bayesian Monte Carlo methods in the analysis of gravitational wave data with an overview of the Bayesian signal detection and estimation methods and demonstration by a couple of simplified examples.
Adaptive Dynamic Bayesian Networks
Ng, B M
2007-10-26
A discrete-time Markov process can be compactly modeled as a dynamic Bayesian network (DBN)--a graphical model with nodes representing random variables and directed edges indicating causality between variables. Each node has a probability distribution, conditional on the variables represented by the parent nodes. A DBN's graphical structure encodes fixed conditional dependencies between variables. But in real-world systems, conditional dependencies between variables may be unknown a priori or may vary over time. Model errors can result if the DBN fails to capture all possible interactions between variables. Thus, we explore the representational framework of adaptive DBNs, whose structure and parameters can change from one time step to the next: a distribution's parameters and its set of conditional variables are dynamic. This work builds on recent work in nonparametric Bayesian modeling, such as hierarchical Dirichlet processes, infinite-state hidden Markov networks and structured priors for Bayes net learning. In this paper, we will explain the motivation for our interest in adaptive DBNs, show how popular nonparametric methods are combined to formulate the foundations for adaptive DBNs, and present preliminary results.
Bayesian analysis toolkit - BAT
Statistical treatment of data is an essential part of any data analysis and interpretation. Different statistical methods and approaches can be used, however the implementation of these approaches is complicated and at times inefficient. The Bayesian analysis toolkit (BAT) is a software package developed in C++ framework that facilitates the statistical analysis of the data using Bayesian theorem. The tool evaluates the posterior probability distributions for models and their parameters using Markov Chain Monte Carlo which in turn provide straightforward parameter estimation, limit setting and uncertainty propagation. Additional algorithms, such as simulated annealing, allow extraction of the global mode of the posterior. BAT sets a well-tested environment for flexible model definition and also includes a set of predefined models for standard statistical problems. The package is interfaced to other software packages commonly used in high energy physics, such as ROOT, Minuit, RooStats and CUBA. We present a general overview of BAT and its algorithms. A few physics examples are shown to introduce the spectrum of its applications. In addition, new developments and features are summarized.
Nuclear spin relaxation in liquids theory, experiments, and applications
Kowalewski, Jozef
2006-01-01
Nuclear magnetic resonance (NMR) is widely used across many fields because of the rich data it produces, and some of the most valuable data come from the study of nuclear spin relaxation in solution. While described to varying degrees in all major NMR books, spin relaxation is often perceived as a difficult, if not obscure, topic, and an accessible, cohesive treatment has been nearly impossible to find.Collecting relaxation theory, experimental techniques, and illustrative applications into a single volume, this book clarifies the nature of the phenomenon, shows how to study it, and explains why such studies are worthwhile. Coverage ranges from basic to rigorous theory and from simple to sophisticated experimental methods, and the level of detail is somewhat greater than most other NMR texts. Topics include cross-relaxation, multispin phenomena, relaxation studies of molecular dynamics and structure, and special topics such as relaxation in systems with quadrupolar nuclei and paramagnetic systems.Avoiding ove...
Book review: Bayesian analysis for population ecology
Link, William A.
2011-01-01
Brian Dennis described the field of ecology as “fertile, uncolonized ground for Bayesian ideas.” He continued: “The Bayesian propagule has arrived at the shore. Ecologists need to think long and hard about the consequences of a Bayesian ecology. The Bayesian outlook is a successful competitor, but is it a weed? I think so.” (Dennis 2004)
Hartelius, Karsten; Carstensen, Jens Michael
2003-01-01
A method for locating distorted grid structures in images is presented. The method is based on the theories of template matching and Bayesian image restoration. The grid is modeled as a deformable template. Prior knowledge of the grid is described through a Markov random field (MRF) model which...... represents the spatial coordinates of the grid nodes. Knowledge of how grid nodes are depicted in the observed image is described through the observation model. The prior consists of a node prior and an arc (edge) prior, both modeled as Gaussian MRFs. The node prior models variations in the positions of grid...... nodes and the arc prior models variations in row and column spacing across the grid. Grid matching is done by placing an initial rough grid over the image and applying an ensemble annealing scheme to maximize the posterior distribution of the grid. The method can be applied to noisy images with missing...
Kobayashi, T
1993-01-01
Conjugated polymers are attractive from the viewpoint of possible applications as novel nonlinear optical materials and conductive materials. They are also very important as a group of materials of one dimensionality. The progress of research in this field is very rapid. At the present stage it is extremely useful to have review articles giving information on the most recent progress.Relaxation in Polymers contains state-of-the-art reviews on: ultrafast responses in various conjugated polymers with large optical nonlinearity; ultrafast relaxation in polysilanes; electronic properties of polysi
Hydrogen relaxation in lutetium
Vajda, P.; Daou, J.N.; Moser, P.
1983-01-01
The internal friction and the dynamic modulus have been measured between 4.2 and 470 K in the system α-LuH(D)x, with x = 0 to 0.2. In well annealed specimens, an (H)-peak is observed at 215-225 K, which has a linearly x-dependent amplitude and exhibits an isotope effect on its activation energy and relaxation time. It is attributed to a Snoek-like relaxation of H-H pairs reorienting in the Lu-lattice. The isotope effect is interpreted in a model of tunnelling from different excited levels for...
A Bayesian variable selection procedure for ranking overlapping gene sets
Skarman, Axel; Mahdi Shariati, Mohammad; Janss, Luc;
2012-01-01
data to study how the variable selection method was affected by overlaps among the pathways. In addition, we compared our approach to another that ignores the overlaps, and studied the differences in the prioritization. The variable selection method was robust to a change in prior probability...... described. In many cases, these methods test one gene set at a time, and therefore do not consider overlaps among the pathways. Here, we present a Bayesian variable selection method to prioritize gene sets that overcomes this limitation by considering all gene sets simultaneously. We applied Bayesian...... variable selection to differential expression to prioritize the molecular and genetic pathways involved in the responses to Escherichia coli infection in Danish Holstein cows. Results We used a Bayesian variable selection method to prioritize Kyoto Encyclopedia of Genes and Genomes pathways. We used our...
Current trends in Bayesian methodology with applications
Upadhyay, Satyanshu K; Dey, Dipak K; Loganathan, Appaia
2015-01-01
Collecting Bayesian material scattered throughout the literature, Current Trends in Bayesian Methodology with Applications examines the latest methodological and applied aspects of Bayesian statistics. The book covers biostatistics, econometrics, reliability and risk analysis, spatial statistics, image analysis, shape analysis, Bayesian computation, clustering, uncertainty assessment, high-energy astrophysics, neural networking, fuzzy information, objective Bayesian methodologies, empirical Bayes methods, small area estimation, and many more topics.Each chapter is self-contained and focuses on
Bayesian Methods and Universal Darwinism
Campbell, John
2010-01-01
Bayesian methods since the time of Laplace have been understood by their practitioners as closely aligned to the scientific method. Indeed a recent champion of Bayesian methods, E. T. Jaynes, titled his textbook on the subject Probability Theory: the Logic of Science. Many philosophers of science including Karl Popper and Donald Campbell have interpreted the evolution of Science as a Darwinian process consisting of a 'copy with selective retention' algorithm abstracted from Darwin's theory of...
Portfolio Allocation for Bayesian Optimization
Brochu, Eric; Hoffman, Matthew W.; De Freitas, Nando
2010-01-01
Bayesian optimization with Gaussian processes has become an increasingly popular tool in the machine learning community. It is efficient and can be used when very little is known about the objective function, making it popular in expensive black-box optimization scenarios. It uses Bayesian methods to sample the objective efficiently using an acquisition function which incorporates the model's estimate of the objective and the uncertainty at any given point. However, there are several differen...
Neuronanatomy, neurology and Bayesian networks
Bielza Lozoya, Maria Concepcion
2014-01-01
Bayesian networks are data mining models with clear semantics and a sound theoretical foundation. In this keynote talk we will pinpoint a number of neuroscience problems that can be addressed using Bayesian networks. In neuroanatomy, we will show computer simulation models of dendritic trees and classification of neuron types, both based on morphological features. In neurology, we will present the search for genetic biomarkers in Alzheimer's disease and the prediction of health-related qualit...
Bayesian Networks and Influence Diagrams
Kjærulff, Uffe Bro; Madsen, Anders Læsø
Probabilistic networks, also known as Bayesian networks and influence diagrams, have become one of the most promising technologies in the area of applied artificial intelligence, offering intuitive, efficient, and reliable methods for diagnosis, prediction, decision making, classification......, troubleshooting, and data mining under uncertainty. Bayesian Networks and Influence Diagrams: A Guide to Construction and Analysis provides a comprehensive guide for practitioners who wish to understand, construct, and analyze intelligent systems for decision support based on probabilistic networks. Intended...
Dale Poirier
2008-01-01
This paper provides Bayesian rationalizations for White’s heteroskedastic consistent (HC) covariance estimator and various modifications of it. An informed Bayesian bootstrap provides the statistical framework.
... Consumers Consumer Information by Audience For Women Hair Dye and Hair Relaxers Share Tweet Linkedin Pin it More sharing ... products. If you have a bad reaction to hair dyes and relaxers, you should: Stop using the product. ...
Nonparametric Bayesian Classification
Coram, M A
2002-01-01
A Bayesian approach to the classification problem is proposed in which random partitions play a central role. It is argued that the partitioning approach has the capacity to take advantage of a variety of large-scale spatial structures, if they are present in the unknown regression function $f_0$. An idealized one-dimensional problem is considered in detail. The proposed nonparametric prior uses random split points to partition the unit interval into a random number of pieces. This prior is found to provide a consistent estimate of the regression function in the $\\L^p$ topology, for any $1 \\leq p < \\infty$, and for arbitrary measurable $f_0:[0,1] \\rightarrow [0,1]$. A Markov chain Monte Carlo (MCMC) implementation is outlined and analyzed. Simulation experiments are conducted to show that the proposed estimate compares favorably with a variety of conventional estimators. A striking resemblance between the posterior mean estimate and the bagged CART estimate is noted and discussed. For higher dimensions, a ...
BAT - Bayesian Analysis Toolkit
One of the most vital steps in any data analysis is the statistical analysis and comparison with the prediction of a theoretical model. The many uncertainties associated with the theoretical model and the observed data require a robust statistical analysis tool. The Bayesian Analysis Toolkit (BAT) is a powerful statistical analysis software package based on Bayes' Theorem, developed to evaluate the posterior probability distribution for models and their parameters. It implements Markov Chain Monte Carlo to get the full posterior probability distribution that in turn provides a straightforward parameter estimation, limit setting and uncertainty propagation. Additional algorithms, such as Simulated Annealing, allow to evaluate the global mode of the posterior. BAT is developed in C++ and allows for a flexible definition of models. A set of predefined models covering standard statistical cases are also included in BAT. It has been interfaced to other commonly used software packages such as ROOT, Minuit, RooStats and CUBA. An overview of the software and its algorithms is provided along with several physics examples to cover a range of applications of this statistical tool. Future plans, new features and recent developments are briefly discussed.
Dielectric Relaxation of Hexadeutero Dimethylsulfoxide
Betting, H.; Stockhausen, M.
1999-11-01
The dielectric relaxation parameters of the title substance (DMSO-d6) in its pure liquid state are determined from meas-urements up to 72 GHz at 20°C in comparison to protonated DMSO. While the relaxation strengths do not differ, the relax-ation time of DMSO-d 6 is significantly longer (21.3 ps) than that of DMSO (19.5 ps).
Experiments in paramagnetic relaxation
This thesis presents two attempts to improve the resolving power of the relaxation measurement technique. The first attempt reconsiders the old technique of steady state saturation. When used in conjunction with the pulse technique, it offers the possibility of obtaining additional information about the system in which all-time derivatives are zero; in addition, non-linear effects may be distinguished from each other. The second attempt involved a systematic study of only one system: Cu in the Tutton salts (K and Rb). The systematic approach, the high accuracy of the measurement and the sheer amount of experimental data for varying temperature, magnetic field and concentration made it possible in this case to separate the prevailing relaxation mechanisms reliably
Nonlinear fractional relaxation
A Tofighi
2012-04-01
We deﬁne a nonlinear model for fractional relaxation phenomena. We use -expansion method to analyse this model. By studying the fundamental solutions of this model we ﬁnd that when → 0 the model exhibits a fast decay rate and when → ∞ the model exhibits a power-law decay. By analysing the frequency response we ﬁnd a logarithmic enhancement for the relative ratio of susceptibility.
Relaxation from particle production
Hook, Anson
2016-01-01
We consider using particle production as a friction force by which to implement a "Relaxion" solution to the electroweak hierarchy problem. Using this approach, we are able to avoid superplanckian field excursions and avoid any conflict with the strong CP problem. The relaxation mechanism can work before, during or after inflation allowing for inflationary dynamics to play an important role or to be completely decoupled.
Bayesian seismic AVO inversion
Buland, Arild
2002-07-01
A new linearized AVO inversion technique is developed in a Bayesian framework. The objective is to obtain posterior distributions for P-wave velocity, S-wave velocity and density. Distributions for other elastic parameters can also be assessed, for example acoustic impedance, shear impedance and P-wave to S-wave velocity ratio. The inversion algorithm is based on the convolutional model and a linearized weak contrast approximation of the Zoeppritz equation. The solution is represented by a Gaussian posterior distribution with explicit expressions for the posterior expectation and covariance, hence exact prediction intervals for the inverted parameters can be computed under the specified model. The explicit analytical form of the posterior distribution provides a computationally fast inversion method. Tests on synthetic data show that all inverted parameters were almost perfectly retrieved when the noise approached zero. With realistic noise levels, acoustic impedance was the best determined parameter, while the inversion provided practically no information about the density. The inversion algorithm has also been tested on a real 3-D dataset from the Sleipner Field. The results show good agreement with well logs but the uncertainty is high. The stochastic model includes uncertainties of both the elastic parameters, the wavelet and the seismic and well log data. The posterior distribution is explored by Markov chain Monte Carlo simulation using the Gibbs sampler algorithm. The inversion algorithm has been tested on a seismic line from the Heidrun Field with two wells located on the line. The uncertainty of the estimated wavelet is low. In the Heidrun examples the effect of including uncertainty of the wavelet and the noise level was marginal with respect to the AVO inversion results. We have developed a 3-D linearized AVO inversion method with spatially coupled model parameters where the objective is to obtain posterior distributions for P-wave velocity, S
Bayesian modeling using WinBUGS
Ntzoufras, Ioannis
2009-01-01
A hands-on introduction to the principles of Bayesian modeling using WinBUGS Bayesian Modeling Using WinBUGS provides an easily accessible introduction to the use of WinBUGS programming techniques in a variety of Bayesian modeling settings. The author provides an accessible treatment of the topic, offering readers a smooth introduction to the principles of Bayesian modeling with detailed guidance on the practical implementation of key principles. The book begins with a basic introduction to Bayesian inference and the WinBUGS software and goes on to cover key topics, including: Markov Chain Monte Carlo algorithms in Bayesian inference Generalized linear models Bayesian hierarchical models Predictive distribution and model checking Bayesian model and variable evaluation Computational notes and screen captures illustrate the use of both WinBUGS as well as R software to apply the discussed techniques. Exercises at the end of each chapter allow readers to test their understanding of the presented concepts and all ...
Dielectric relaxation and hydrogen diffusion in amorphous silicon
Phillips, J.C. (AT and T Bell Labs., Murray Hill, NJ (United States))
1994-04-01
Hydrogen diffusion is technologically critical to the processing of amorphous Si for solar cell applications. It is shown that this diffusion belongs to a broad class of dielectric relaxation mechanisms which were first studied by Kohlrausch in 1847. A microscopic theory of the Kohlrausch relaxation constant [beta][sub K] is also constructed. This theory explains the values of [beta] observed in many electronic, molecular and polymeric relaxation processes. It is based on two novel concepts: Wiener sausages, from statistical mechanics, and the magic wand, from axiomatic set theory
Tang, An-Min; Tang, Nian-Sheng
2015-02-28
We propose a semiparametric multivariate skew-normal joint model for multivariate longitudinal and multivariate survival data. One main feature of the posited model is that we relax the commonly used normality assumption for random effects and within-subject error by using a centered Dirichlet process prior to specify the random effects distribution and using a multivariate skew-normal distribution to specify the within-subject error distribution and model trajectory functions of longitudinal responses semiparametrically. A Bayesian approach is proposed to simultaneously obtain Bayesian estimates of unknown parameters, random effects and nonparametric functions by combining the Gibbs sampler and the Metropolis-Hastings algorithm. Particularly, a Bayesian local influence approach is developed to assess the effect of minor perturbations to within-subject measurement error and random effects. Several simulation studies and an example are presented to illustrate the proposed methodologies. PMID:25404574
Probability biases as Bayesian inference
Andre; C. R. Martins
2006-11-01
Full Text Available In this article, I will show how several observed biases in human probabilistic reasoning can be partially explained as good heuristics for making inferences in an environment where probabilities have uncertainties associated to them. Previous results show that the weight functions and the observed violations of coalescing and stochastic dominance can be understood from a Bayesian point of view. We will review those results and see that Bayesian methods should also be used as part of the explanation behind other known biases. That means that, although the observed errors are still errors under the be understood as adaptations to the solution of real life problems. Heuristics that allow fast evaluations and mimic a Bayesian inference would be an evolutionary advantage, since they would give us an efficient way of making decisions. %XX In that sense, it should be no surprise that humans reason with % probability as it has been observed.
Bayesian Methods and Universal Darwinism
Campbell, John
2010-01-01
Bayesian methods since the time of Laplace have been understood by their practitioners as closely aligned to the scientific method. Indeed a recent champion of Bayesian methods, E. T. Jaynes, titled his textbook on the subject Probability Theory: the Logic of Science. Many philosophers of science including Karl Popper and Donald Campbell have interpreted the evolution of Science as a Darwinian process consisting of a 'copy with selective retention' algorithm abstracted from Darwin's theory of Natural Selection. Arguments are presented for an isomorphism between Bayesian Methods and Darwinian processes. Universal Darwinism, as the term has been developed by Richard Dawkins, Daniel Dennett and Susan Blackmore, is the collection of scientific theories which explain the creation and evolution of their subject matter as due to the operation of Darwinian processes. These subject matters span the fields of atomic physics, chemistry, biology and the social sciences. The principle of Maximum Entropy states that system...
Bayesian methods for proteomic biomarker development
Belinda Hernández
2015-12-01
In this review we provide an introduction to Bayesian inference and demonstrate some of the advantages of using a Bayesian framework. We summarize how Bayesian methods have been used previously in proteomics and other areas of bioinformatics. Finally, we describe some popular and emerging Bayesian models from the statistical literature and provide a worked tutorial including code snippets to show how these methods may be applied for the evaluation of proteomic biomarkers.
Bayesian variable selection and data integration for biological regulatory networks
Jensen, Shane T; Chen, Guang; Stoeckert, Jr, Christian J.
2007-01-01
A substantial focus of research in molecular biology are gene regulatory networks: the set of transcription factors and target genes which control the involvement of different biological processes in living cells. Previous statistical approaches for identifying gene regulatory networks have used gene expression data, ChIP binding data or promoter sequence data, but each of these resources provides only partial information. We present a Bayesian hierarchical model that integrates all three dat...
Bayesian test and Kuhn's paradigm
Chen Xiaoping
2006-01-01
Kuhn's theory of paradigm reveals a pattern of scientific progress,in which normal science alternates with scientific revolution.But Kuhn underrated too much the function of scientific test in his pattern,because he focuses all his attention on the hypothetico-deductive schema instead of Bayesian schema.This paper employs Bayesian schema to re-examine Kuhn's theory of paradigm,to uncover its logical and rational components,and to illustrate the tensional structure of logic and belief,rationality and irrationality,in the process of scientific revolution.
3D Bayesian contextual classifiers
Larsen, Rasmus
2000-01-01
We extend a series of multivariate Bayesian 2-D contextual classifiers to 3-D by specifying a simultaneous Gaussian distribution for the feature vectors as well as a prior distribution of the class variables of a pixel and its 6 nearest 3-D neighbours.......We extend a series of multivariate Bayesian 2-D contextual classifiers to 3-D by specifying a simultaneous Gaussian distribution for the feature vectors as well as a prior distribution of the class variables of a pixel and its 6 nearest 3-D neighbours....
Bayesian Model Averaging for Propensity Score Analysis
Kaplan, David; Chen, Jianshen
2013-01-01
The purpose of this study is to explore Bayesian model averaging in the propensity score context. Previous research on Bayesian propensity score analysis does not take into account model uncertainty. In this regard, an internally consistent Bayesian framework for model building and estimation must also account for model uncertainty. The…
Bayesian networks and food security - An introduction
Stein, A.
2004-01-01
This paper gives an introduction to Bayesian networks. Networks are defined and put into a Bayesian context. Directed acyclical graphs play a crucial role here. Two simple examples from food security are addressed. Possible uses of Bayesian networks for implementation and further use in decision sup
Bayesian variable order Markov models: Towards Bayesian predictive state representations
C. Dimitrakakis
2009-01-01
We present a Bayesian variable order Markov model that shares many similarities with predictive state representations. The resulting models are compact and much easier to specify and learn than classical predictive state representations. Moreover, we show that they significantly outperform a more st
Vinther, Jakob; Sperling, Erik A; Briggs, Derek E G; Peterson, Kevin J
2012-04-01
Aplacophorans have long been argued to be basal molluscs. We present a molecular phylogeny, including the aplacophorans Neomeniomorpha (Solenogastres) and Chaetodermomorpha (Caudofoveata), which recovered instead the clade Aculifera (Aplacophora + Polyplacophora). Our relaxed Bayesian molecular clock estimates an Early Ordovician appearance of the aculiferan crown group consistent with the presence of chiton-like molluscs with seven or eight dorsal shell plates by the Late Cambrian (approx. 501-490 Ma). Molecular, embryological and palaeontological data indicate that aplacophorans, as well as chitons, evolved from a paraphyletic assemblage of chiton-like ancestors. The recovery of cephalopods as a sister group to aculiferans suggests that the plesiomorphic condition in molluscs might be a morphology similar to that found in monoplacophorans. PMID:21976685
Bayesian Analysis of Experimental Data
Lalmohan Bhar
2013-10-01
Full Text Available Analysis of experimental data from Bayesian point of view has been considered. Appropriate methodology has been developed for application into designed experiments. Normal-Gamma distribution has been considered for prior distribution. Developed methodology has been applied to real experimental data taken from long term fertilizer experiments.
Bayesian image restoration, using configurations
Thorarinsdottir, Thordis Linda
2006-01-01
configurations are expressed in terms of the mean normal measure of the random set. These probabilities are used as prior probabilities in a Bayesian image restoration approach. Estimation of the remaining parameters in the model is outlined for the salt and pepper noise. The inference in the model is discussed...
Bayesian image restoration, using configurations
Thorarinsdottir, Thordis
configurations are expressed in terms of the mean normal measure of the random set. These probabilities are used as prior probabilities in a Bayesian image restoration approach. Estimation of the remaining parameters in the model is outlined for salt and pepper noise. The inference in the model is discussed in...
ANALYSIS OF BAYESIAN CLASSIFIER ACCURACY
Felipe Schneider Costa
2013-01-01
Full Text Available The naÃ¯ve Bayes classifier is considered one of the most effective classification algorithms today, competing with more modern and sophisticated classifiers. Despite being based on unrealistic (naÃ¯ve assumption that all variables are independent, given the output class, the classifier provides proper results. However, depending on the scenario utilized (network structure, number of samples or training cases, number of variables, the network may not provide appropriate results. This study uses a process variable selection, using the chi-squared test to verify the existence of dependence between variables in the data model in order to identify the reasons which prevent a Bayesian network to provide good performance. A detailed analysis of the data is also proposed, unlike other existing work, as well as adjustments in case of limit values between two adjacent classes. Furthermore, variable weights are used in the calculation of a posteriori probabilities, calculated with mutual information function. Tests were applied in both a naÃ¯ve Bayesian network and a hierarchical Bayesian network. After testing, a significant reduction in error rate has been observed. The naÃ¯ve Bayesian network presented a drop in error rates from twenty five percent to five percent, considering the initial results of the classification process. In the hierarchical network, there was not only a drop in fifteen percent error rate, but also the final result came to zero.
Bayesian Agglomerative Clustering with Coalescents
Teh, Yee Whye; Daumé III, Hal; Roy, Daniel
2009-01-01
We introduce a new Bayesian model for hierarchical clustering based on a prior over trees called Kingman's coalescent. We develop novel greedy and sequential Monte Carlo inferences which operate in a bottom-up agglomerative fashion. We show experimentally the superiority of our algorithms over others, and demonstrate our approach in document clustering and phylolinguistics.
Bayesian Networks and Influence Diagrams
Kjærulff, Uffe Bro; Madsen, Anders Læsø
Bayesian Networks and Influence Diagrams: A Guide to Construction and Analysis, Second Edition, provides a comprehensive guide for practitioners who wish to understand, construct, and analyze intelligent systems for decision support based on probabilistic networks. This new edition contains six new...
Topics in Bayesian statistics and maximum entropy
Notions of Bayesian decision theory and maximum entropy methods are reviewed with particular emphasis on probabilistic inference and Bayesian modeling. The axiomatic approach is considered as the best justification of Bayesian analysis and maximum entropy principle applied in natural sciences. Particular emphasis is put on solving the inverse problem in digital image restoration and Bayesian modeling of neural networks. Further topics addressed briefly include language modeling, neutron scattering, multiuser detection and channel equalization in digital communications, genetic information, and Bayesian court decision-making. (author)
Bayesian analysis of rare events
Straub, Daniel; Papaioannou, Iason; Betz, Wolfgang
2016-06-01
In many areas of engineering and science there is an interest in predicting the probability of rare events, in particular in applications related to safety and security. Increasingly, such predictions are made through computer models of physical systems in an uncertainty quantification framework. Additionally, with advances in IT, monitoring and sensor technology, an increasing amount of data on the performance of the systems is collected. This data can be used to reduce uncertainty, improve the probability estimates and consequently enhance the management of rare events and associated risks. Bayesian analysis is the ideal method to include the data into the probabilistic model. It ensures a consistent probabilistic treatment of uncertainty, which is central in the prediction of rare events, where extrapolation from the domain of observation is common. We present a framework for performing Bayesian updating of rare event probabilities, termed BUS. It is based on a reinterpretation of the classical rejection-sampling approach to Bayesian analysis, which enables the use of established methods for estimating probabilities of rare events. By drawing upon these methods, the framework makes use of their computational efficiency. These methods include the First-Order Reliability Method (FORM), tailored importance sampling (IS) methods and Subset Simulation (SuS). In this contribution, we briefly review these methods in the context of the BUS framework and investigate their applicability to Bayesian analysis of rare events in different settings. We find that, for some applications, FORM can be highly efficient and is surprisingly accurate, enabling Bayesian analysis of rare events with just a few model evaluations. In a general setting, BUS implemented through IS and SuS is more robust and flexible.
Bayesian methods for measures of agreement
Broemeling, Lyle D
2009-01-01
Using WinBUGS to implement Bayesian inferences of estimation and testing hypotheses, Bayesian Methods for Measures of Agreement presents useful methods for the design and analysis of agreement studies. It focuses on agreement among the various players in the diagnostic process.The author employs a Bayesian approach to provide statistical inferences based on various models of intra- and interrater agreement. He presents many examples that illustrate the Bayesian mode of reasoning and explains elements of a Bayesian application, including prior information, experimental information, the likelihood function, posterior distribution, and predictive distribution. The appendices provide the necessary theoretical foundation to understand Bayesian methods as well as introduce the fundamentals of programming and executing the WinBUGS software.Taking a Bayesian approach to inference, this hands-on book explores numerous measures of agreement, including the Kappa coefficient, the G coefficient, and intraclass correlation...
Plug & Play object oriented Bayesian networks
Bangsø, Olav; Flores, J.; Jensen, Finn Verner
2003-01-01
Object oriented Bayesian networks have proven themselves useful in recent years. The idea of applying an object oriented approach to Bayesian networks has extended their scope to larger domains that can be divided into autonomous but interrelated entities. Object oriented Bayesian networks have...... been shown to be quite suitable for dynamic domains as well. However, processing object oriented Bayesian networks in practice does not take advantage of their modular structure. Normally the object oriented Bayesian network is transformed into a Bayesian network and, inference is performed...... by constructing a junction tree from this network. In this paper we propose a method for translating directly from object oriented Bayesian networks to junction trees, avoiding the intermediate translation. We pursue two main purposes: firstly, to maintain the original structure organized in an instance tree...
Coherent effects and relaxation processes in liquid potassium
The coherent dynamic structure factor of liquid potassium has been obtained from inelastic neutron scattering data at temperatures of 340, 440 and 550 K. The parts of dispersion curves for collective excitations have been plotted and some of their characteristics have been analysed. Represented in relative units, our experimental points are in an agreement with the ones for liquid rubidium and cesium. The molecular memory effects are described within a framework of theoretical representations of a spatial dispersion for the relaxation parameter of non-Markovian process. It has been found that molecular memory effects are important for relaxation processes which are represented in inelastic both coherent and incoherent neutron scattering. (orig.)
Flexible Bayesian Nonparametric Priors and Bayesian Computational Methods
Zhu, Weixuan
2016-01-01
The definition of vectors of dependent random probability measures is a topic of interest in Bayesian nonparametrics. They represent dependent nonparametric prior distributions that are useful for modelling observables for which specific covariate values are known. Our first contribution is the introduction of novel multivariate vectors of two-parameter Poisson-Dirichlet process. The dependence is induced by applying a L´evy copula to the marginal L´evy intensities. Our attenti...
Magnetic relaxation in anisotropic magnets
Lindgård, Per-Anker
1971-01-01
The line shape and the kinematic and thermodynamic slowing down of the critical and paramagnetic relaxation in axially anisotropic materials are discussed. Kinematic slowing down occurs only in the longitudinal relaxation function. The thermodynamic slowing down occurs in either the transverse or...
Temperature Relaxation in Hot Dense Hydrogen
Murillo, Michael S.; Dharma-wardana, M. W. C.
2007-01-01
Temperature equilibration of hydrogen is studied for conditions relevant to inertial confinement fusion. New molecular-dynamics simulations and results from quantum many-body theory are compared with Landau-Spitzer (LS) predictions for temperatures T from 50 eV to 5000 eV, and densities with Wigner-Seitz radii r_s = 1.0 and 0.5. The relaxation is slower than the LS result, even for temperatures in the keV range, but converges to agreement in the high-T limit.
Structural relaxation of amorphous silicon carbide
We have examined amorphous structures of silicon carbide (SiC) using both transmission electron microscopy and a molecular-dynamics approach. Radial distribution functions revealed that amorphous SiC contains not only heteronuclear (Si-C) bonds but also homonuclear (Si-Si and C-C) bonds. The ratio of heteronuclear to homonuclear bonds was found to change upon annealing, suggesting that structural relaxation of the amorphous SiC occurred. Good agreement was obtained between the simulated and experimentally measured radial distribution functions
Structural relaxation of amorphous silicon carbide.
Ishimaru, Manabu; Bae, In-Tae; Hirotsu, Yoshihiko; Matsumura, Syo; Sickafus, Kurt E
2002-07-29
We have examined amorphous structures of silicon carbide (SiC) using both transmission electron microscopy and a molecular-dynamics approach. Radial distribution functions revealed that amorphous SiC contains not only heteronuclear (Si-C) bonds but also homonuclear (Si-Si and C-C) bonds. The ratio of heteronuclear to homonuclear bonds was found to change upon annealing, suggesting that structural relaxation of the amorphous SiC occurred. Good agreement was obtained between the simulated and experimentally measured radial distribution functions. PMID:12144449
Excited-state relaxation of some aminoquinolines
B. M. Uzhinov
2006-04-01
Full Text Available The absorption and fluorescence spectra, fluorescence quantum yields and lifetimes, and fluorescence rate constants (kf of 2-amino-3-(2Ã¢Â€Â²-benzoxazolylquinoline (I, 2-amino-3-(2Ã¢Â€Â²-benzothiazolylquinoline (II, 2-amino-3-(2Ã¢Â€Â²-methoxybenzothiazolyl-quinoline (III, 2-amino-3-(2Ã¢Â€Â²-benzothiazolylbenzoquinoline (IV at different temperatures have been measured. The shortwavelength shift of fluorescence spectra of compounds studied (23Ã¢Â€Â“49 nm in ethanol as the temperature decreases (the solvent viscosity increases points out that the excited-state relaxation process takes place. The rate of this process depends essentially on the solvent viscosity, but not the solvent polarity. The essential increasing of fluorescence rate constant kf (up to about 7 times as the solvent viscosity increases proves the existence of excited-state structural relaxation consisting in the mutual internal rotation of molecular fragments of aminoquinolines studied, followed by the solvent orientational relaxation.
Tsvetkov, N. V.; Mikhailova, M. E.; Lebedeva, E. V.; Lezov, A. A.; Rogozhin, V. B.; Rotinyan, T. A.
2016-03-01
Free relaxation of electric birefringence in tetrachloromethane solution of high molecular weight poly(butyl-isocyanate) was studied. The effect of electric field strength on the average relaxation time was observed. The relaxation spectrum was analyzed using the Rouse and Zimm theories. With increase in the electric field strength, the contribution of fast (deformation) relaxation modes also increased significantly. It is assumed that certain changes in intramolecular mobility occur under the influence of electric field.
Bayesian approach to rough set
Marwala, Tshilidzi
2007-01-01
This paper proposes an approach to training rough set models using Bayesian framework trained using Markov Chain Monte Carlo (MCMC) method. The prior probabilities are constructed from the prior knowledge that good rough set models have fewer rules. Markov Chain Monte Carlo sampling is conducted through sampling in the rough set granule space and Metropolis algorithm is used as an acceptance criteria. The proposed method is tested to estimate the risk of HIV given demographic data. The results obtained shows that the proposed approach is able to achieve an average accuracy of 58% with the accuracy varying up to 66%. In addition the Bayesian rough set give the probabilities of the estimated HIV status as well as the linguistic rules describing how the demographic parameters drive the risk of HIV.
Attention in a bayesian framework
Whiteley, Louise Emma; Sahani, Maneesh
2012-01-01
include both selective phenomena, where attention is invoked by cues that point to particular stimuli, and integrative phenomena, where attention is invoked dynamically by endogenous processing. However, most previous Bayesian accounts of attention have focused on describing relatively simple experimental...... settings, where cues shape expectations about a small number of upcoming stimuli and thus convey "prior" information about clearly defined objects. While operationally consistent with the experiments it seeks to describe, this view of attention as prior seems to miss many essential elements of both its......The behavioral phenomena of sensory attention are thought to reflect the allocation of a limited processing resource, but there is little consensus on the nature of the resource or why it should be limited. Here we argue that a fundamental bottleneck emerges naturally within Bayesian models of...
Bayesian Sampling using Condition Indicators
Faber, Michael H.; Sørensen, John Dalsgaard
2002-01-01
allows for a Bayesian formulation of the indicators whereby the experience and expertise of the inspection personnel may be fully utilized and consistently updated as frequentistic information is collected. The approach is illustrated on an example considering a concrete structure subject to corrosion......The problem of control quality of components is considered for the special case where the acceptable failure rate is low, the test costs are high and where it may be difficult or impossible to test the condition of interest directly. Based on the classical control theory and the concept of...... condition indicators introduced by Benjamin and Cornell (1970) a Bayesian approach to quality control is formulated. The formulation is then extended to the case where the quality control is based on sampling of indirect information about the condition of the components, i.e. condition indicators. This...
BAYESIAN IMAGE RESTORATION, USING CONFIGURATIONS
Thordis Linda Thorarinsdottir
2011-05-01
Full Text Available In this paper, we develop a Bayesian procedure for removing noise from images that can be viewed as noisy realisations of random sets in the plane. The procedure utilises recent advances in configuration theory for noise free random sets, where the probabilities of observing the different boundary configurations are expressed in terms of the mean normal measure of the random set. These probabilities are used as prior probabilities in a Bayesian image restoration approach. Estimation of the remaining parameters in the model is outlined for salt and pepper noise. The inference in the model is discussed in detail for 3 X 3 and 5 X 5 configurations and examples of the performance of the procedure are given.
Bayesian Seismology of the Sun
Gruberbauer, Michael
2013-01-01
We perform a Bayesian grid-based analysis of the solar l=0,1,2 and 3 p modes obtained via BiSON in order to deliver the first Bayesian asteroseismic analysis of the solar composition problem. We do not find decisive evidence to prefer either of the contending chemical compositions, although the revised solar abundances (AGSS09) are more probable in general. We do find indications for systematic problems in standard stellar evolution models, unrelated to the consequences of inadequate modelling of the outer layers on the higher-order modes. The seismic observables are best fit by solar models that are several hundred million years older than the meteoritic age of the Sun. Similarly, meteoritic age calibrated models do not adequately reproduce the observed seismic observables. Our results suggest that these problems will affect any asteroseismic inference that relies on a calibration to the Sun.
Bayesian priors for transiting planets
Kipping, David M
2016-01-01
As astronomers push towards discovering ever-smaller transiting planets, it is increasingly common to deal with low signal-to-noise ratio (SNR) events, where the choice of priors plays an influential role in Bayesian inference. In the analysis of exoplanet data, the selection of priors is often treated as a nuisance, with observers typically defaulting to uninformative distributions. Such treatments miss a key strength of the Bayesian framework, especially in the low SNR regime, where even weak a priori information is valuable. When estimating the parameters of a low-SNR transit, two key pieces of information are known: (i) the planet has the correct geometric alignment to transit and (ii) the transit event exhibits sufficient signal-to-noise to have been detected. These represent two forms of observational bias. Accordingly, when fitting transits, the model parameter priors should not follow the intrinsic distributions of said terms, but rather those of both the intrinsic distributions and the observational ...
Bayesian Inference for Radio Observations
Lochner, Michelle; Zwart, Jonathan T L; Smirnov, Oleg; Bassett, Bruce A; Oozeer, Nadeem; Kunz, Martin
2015-01-01
(Abridged) New telescopes like the Square Kilometre Array (SKA) will push into a new sensitivity regime and expose systematics, such as direction-dependent effects, that could previously be ignored. Current methods for handling such systematics rely on alternating best estimates of instrumental calibration and models of the underlying sky, which can lead to inaccurate uncertainty estimates and biased results because such methods ignore any correlations between parameters. These deconvolution algorithms produce a single image that is assumed to be a true representation of the sky, when in fact it is just one realisation of an infinite ensemble of images compatible with the noise in the data. In contrast, here we report a Bayesian formalism that simultaneously infers both systematics and science. Our technique, Bayesian Inference for Radio Observations (BIRO), determines all parameters directly from the raw data, bypassing image-making entirely, by sampling from the joint posterior probability distribution. Thi...