Comparing correlations of continuous observations from two independent populations using a sequential approach

A sequential study design generally makes more efficient use of available information than a fixed sample counterpart of equal power. This feature is gradually being exploited by researchers in genetic and epidemiological investigations that utilize banked biological resources and in studies where time, cost and ethics are prominent considerations. Recent work in this area has focussed on the sequential analysis of matched case-control studies with a dichotomous trait. In this paper, we extend the sequential approach to a comparison of the associations within two independent groups of paired continuous observations. Such a comparison is particularly relevant in familial studies of phenotypic correlation using twins. We develop a sequential twin method based on the intraclass correlation and show that use of sequential methodology can lead to a substantial reduction in the number of observations without compromising the study error rates. Additionally, our approach permits straightforward allowance for other explanatory factors in the analysis. We illustrate our method in a sequential heritability study of dysplasia that allows for the effect of body mass index and compares monozygotes with pairs of singleton sisters. Copyright (c) 2006 John Wiley & Sons, Ltd.

Vibrational energy levels for the electronic ground state of the diazocarbene (CNN) molecule

The vibrational energy levels of diazocarbene (diazomethylene) in its electronic ground state, (X) over tilde (3) Sigma(-) CNN, have been predicted using the variational method. The potential energy surfaces of (X) over tilde (3) A" CNN were determined by employing ab initio single reference coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], multi-reference complete active space self-consistent-field (CASSCF), and internally contracted multi-reference configuration interaction (ICMRCI) methods. The correlation-consistent polarised valence quadruple zeta (cc-pVQZ) basis set was used. Four sets of vibrational energy levels determined from the four distinct analytical potential functions have been compared with the experimental values from the laser-induced fluorescence measurements of Wurfel et al. obtained in 1992. The CCSD, CCSD(T), and CASSCF potentials have not provided satisfactory agreement with the experimental observations. In this light, the importance of both non-dynamic (static) and dynamic correlation effects in describing the ground state of CNN is emphasised. Our best theoretical fundamental frequencies at the cc-pVQZ ICMRCI level of theory, v(1) = 1230, v(2) = 394, and v(3) = 1420 cm(-1) are in excellent agreement with the experimental values of v(1) = 1235, v(2) = 396, and v(3) = 1419cm(-1) and the mean absolute deviation between the 23 calculated and experimental vibrational energy levels is only 7.4 cm(-1). It is shown that the previously suggested observation of the v(3) frequency at about 2847cm(-1) was in fact the first overtone 2v(3).

Spectroscopy of highly excited vibrational states of HCN in its ground electronic state

An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29 000 and 30 000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typically (0,0,4), the nu(3) mode being approximately equivalent to the C-H stretching vibration. Then a second laser is used to search for transitions between this intermediate state and highly vibrationally excited states. When one of these transitions is found, HCN molecules are transferred to a highly excited vibrational state. Third, a ultraviolet laser photodissociates the highly excited molecules to produce H and CN radicals in its A (2)Pi electronic state. Finally, a fourth laser (probe) detects the presence of the CN(A) photofragments by means of an A-->B-->X laser induced fluorescence scheme. The spectra obtained with this technique, consisting of several rotationally resolved vibrational bands, have been analyzed. The positions and rotational parameters of the states observed are presented and compared with the results of a state-of-the-art variational calculation. (C) 2004 American Institute of Physics.

Full-dimensional quantum calculations of ground-state tunneling splitting of malonaldehyde using an accurate ab initio potential energy surface

Quantum calculations of the ground vibrational state tunneling splitting of H-atom and D-atom transfer in malonaldehyde are performed on a full-dimensional ab initio potential energy surface (PES). The PES is a fit to 11 147 near basis-set-limit frozen-core CCSD(T) electronic energies. This surface properly describes the invariance of the potential with respect to all permutations of identical atoms. The saddle-point barrier for the H-atom transfer on the PES is 4.1 kcal/mol, in excellent agreement with the reported ab initio value. Model one-dimensional and "exact" full-dimensional calculations of the splitting for H- and D-atom transfer are done using this PES. The tunneling splittings in full dimensionality are calculated using the unbiased "fixed-node" diffusion Monte Carlo (DMC) method in Cartesian and saddle-point normal coordinates. The ground-state tunneling splitting is found to be 21.6 cm(-1) in Cartesian coordinates and 22.6 cm(-1) in normal coordinates, with an uncertainty of 2-3 cm(-1). This splitting is also calculated based on a model which makes use of the exact single-well zero-point energy (ZPE) obtained with the MULTIMODE code and DMC ZPE and this calculation gives a tunneling splitting of 21-22 cm(-1). The corresponding computed splittings for the D-atom transfer are 3.0, 3.1, and 2-3 cm(-1). These calculated tunneling splittings agree with each other to within less than the standard uncertainties obtained with the DMC method used, which are between 2 and 3 cm(-1), and agree well with the experimental values of 21.6 and 2.9 cm(-1) for the H and D transfer, respectively. (C) 2008 American Institute of Physics.

Classification-based probabilistic modeling of texture transition for fast line search tracking and delineation

We introduce a classification-based approach to finding occluding texture boundaries. The classifier is composed of a set of weak learners, which operate on image intensity discriminative features that are defined on small patches and are fast to compute. A database that is designed to simulate digitized occluding contours of textured objects in natural images is used to train the weak learners. The trained classifier score is then used to obtain a probabilistic model for the presence of texture transitions, which can readily be used for line search texture boundary detection in the direction normal to an initial boundary estimate. This method is fast and therefore suitable for real-time and interactive applications. It works as a robust estimator, which requires a ribbon-like search region and can handle complex texture structures without requiring a large number of observations. We demonstrate results both in the context of interactive 2D delineation and of fast 3D tracking and compare its performance with other existing methods for line search boundary detection.

Bayesian retrieval of complete posterior PDFs of oceanic rain rate from microwave observations

A new Bayesian algorithm for retrieving surface rain rate from Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) over the ocean is presented, along with validations against estimates from the TRMM Precipitation Radar (PR). The Bayesian approach offers a rigorous basis for optimally combining multichannel observations with prior knowledge. While other rain-rate algorithms have been published that are based at least partly on Bayesian reasoning, this is believed to be the first self-contained algorithm that fully exploits Bayes’s theorem to yield not just a single rain rate, but rather a continuous posterior probability distribution of rain rate. To advance the understanding of theoretical benefits of the Bayesian approach, sensitivity analyses have been conducted based on two synthetic datasets for which the “true” conditional and prior distribution are known. Results demonstrate that even when the prior and conditional likelihoods are specified perfectly, biased retrievals may occur at high rain rates. This bias is not the result of a defect of the Bayesian formalism, but rather represents the expected outcome when the physical constraint imposed by the radiometric observations is weak owing to saturation effects. It is also suggested that both the choice of the estimators and the prior information are crucial to the retrieval. In addition, the performance of the Bayesian algorithm herein is found to be comparable to that of other benchmark algorithms in real-world applications, while having the additional advantage of providing a complete continuous posterior probability distribution of surface rain rate.

Mono- and heterodimetallic FeII and RuII complexes based on a novel heteroditopic 4′-{bis(phosphanyl)aryl}-2,2′:6′,2″-terpyridine ligand

In the search for a versatile building block that allows the preparation of heteroditopic tpy-pincer bridging ligands, the synthon 14'-[C6H3(CH2Br)(2)-3,5]-2,2':6',2 ''-terpyridine was synthesized. Facile introduction of diphenylphosphanyl groups in this synthon gave the ligand 14'-[C6H3(CH2PPh2)2-3,5]-2,2':6',2"-terpyridine) ([tpyPC(H)Pj). The asymmetric mononuclear complex [Fe(tpy){tpyPC(H)P}](PF6)(2), prepared by selective coordination of [Fe(tpy)Cl-3] to the tpy moiety of [tpyPC(H)P], was used for the synthesis of the heterodimetallic complex [Fe(tpy)(tpyPCP)Ru(tpy)](PFC,)3, which applies the "complex as ligand" approach. Coordination of the ruthenium centre at the PC(H)P-pincer moiety of [Fe(tpy){tpyPC(H)P}](PF6)(2) has been achieved by applying a transcyclometallation procedure. The ground-state electronic properties of both complexes, investigated by cyclic and square-wave voltammetries and UV/Vis spectroscopy, are discussed and compared with those of [Fe(tPY)(2)](PF6)(2) and [Ru(PCP)(tpy)]Cl, which represent the mononuclear components of the heterodinuclear species. An in situ UV/Vis spectroelectrochemical study was performed in order to localize the oxidation and reduction steps and to gain information about the Fe-II-Ru-II communication in the heterodimetallic system [Fe(tpy)(tpyPCP)Ru(tpy)](PF6)(3) mediated by the bridging ligand [tpyPCP]. Both the voltammetric and spectroelectrochemical results point to only very limited electronic interaction between the metal centres in the ground state.

PETS2010 and PETS2009 evaluation of results using individual ground truthed single views

This paper presents the results of the crowd image analysis challenge of the PETS2010 workshop. The evaluation was carried out using a selection of the metrics developed in the Video Analysis and Content Extraction (VACE) program and the CLassification of Events, Activities, and Relationships (CLEAR) consortium. The PETS 2010 evaluation was performed using new ground truthing create from each independant two dimensional view. In addition, the performance of the submissions to the PETS 2009 and Winter-PETS 2009 were evaluated and included in the results. The evaluation highlights the detection and tracking performance of the authors’ systems in areas such as precision, accuracy and robustness.

Surveillance camera calibration from observations of a pedestrian

Calibrated cameras are an extremely useful resource for computer vision scenarios. Typically, cameras are calibrated through calibration targets, measurements of the observed scene, or self-calibrated through features matched between cameras with overlapping fields of view. This paper considers an approach to camera calibration based on observations of a pedestrian and compares the resulting calibration to a commonly used approach requiring that measurements be made of the scene.

Assessing the accuracy of CME speed and trajectory estimates from STEREO observations through a comparison of independent methods

We have estimated the speed and direction of propagation of a number of Coronal Mass Ejections (CMEs) using single-spacecraft data from the STEREO Heliospheric Imager (HI) wide-field cameras. In general, these values are in good agreement with those predicted by Thernisien, Vourlidas, and Howard in Solar Phys. 256, 111 -aEuro parts per thousand 130 (2009) using a forward modelling method to fit CMEs imaged by the STEREO COR2 coronagraphs. The directions of the CMEs predicted by both techniques are in good agreement despite the fact that many of the CMEs under study travel in directions that cause them to fade rapidly in the HI images. The velocities estimated from both techniques are in general agreement although there are some interesting differences that may provide evidence for the influence of the ambient solar wind on the speed of CMEs. The majority of CMEs with a velocity estimated to be below 400 km s(-1) in the COR2 field of view have higher estimated velocities in the HI field of view, while, conversely, those with COR2 velocities estimated to be above 400 km s(-1) have lower estimated HI velocities. We interpret this as evidence for the deceleration of fast CMEs and the acceleration of slower CMEs by interaction with the ambient solar wind beyond the COR2 field of view. We also show that the uncertainties in our derived parameters are influenced by the range of elongations over which each CME can be tracked. In order to reduce the uncertainty in the predicted arrival time of a CME at 1 Astronomical Unit (AU) to within six hours, the CME needs to be tracked out to at least 30 degrees elongation. This is in good agreement with predictions of the accuracy of our technique based on Monte Carlo simulations.

Physics-based modelling for remote sensing of snow

Remote sensing is the only practicable means to observe snow at large scales. Measurements from passive microwave instruments have been used to derive snow climatology since the late 1970’s, but the algorithms used were limited by the computational power of the era. Simplifications such as the assumption of constant snow properties enabled snow mass to be retrieved from the microwave measurements, but large errors arise from those assumptions, which are still used today. A better approach is to perform retrievals within a data assimilation framework, where a physically-based model of the snow properties can be used to produce the best estimate of the snow cover, in conjunction with multi-sensor observations such as the grain size, surface temperature, and microwave radiation. We have developed an existing snow model, SNOBAL, to incorporate mass and energy transfer of the soil, and to simulate the growth of the snow grains. An evaluation of this model is presented and techniques for the development of new retrieval systems are discussed.

View-based modelling of human visual navigation errors

View-based and Cartesian representations provide rival accounts of visual navigation in humans, and here we explore possible models for the view-based case. A visual “homing” experiment was undertaken by human participants in immersive virtual reality. The distributions of end-point errors on the ground plane differed significantly in shape and extent depending on visual landmark configuration and relative goal location. A model based on simple visual cues captures important characteristics of these distributions. Augmenting visual features to include 3D elements such as stereo and motion parallax result in a set of models that describe the data accurately, demonstrating the effectiveness of a view-based approach.

Measuring the impact of observations on the predictability of the Kuroshio Extension in a shallow-water model

In this paper sequential importance sampling is used to assess the impact of observations on a ensemble prediction for the decadal path transitions of the Kuroshio Extension (KE). This particle filtering approach gives access to the probability density of the state vector, which allows us to determine the predictive power — an entropy based measure — of the ensemble prediction. The proposed set-up makes use of an ensemble that, at each time, samples the climatological probability distribution. Then, in a post-processing step, the impact of different sets of observations is measured by the increase in predictive power of the ensemble over the climatological signal during one-year. The method is applied in an identical-twin experiment for the Kuroshio Extension using a reduced-gravity shallow water model. We investigate the impact of assimilating velocity observations from different locations during the elongated and the contracted meandering state of the KE. Optimal observations location correspond to regions with strong potential vorticity gradients. For the elongated state the optimal location is in the first meander of the KE. During the contracted state of the KE it is located south of Japan, where the Kuroshio separates from the coast.

Large-scale and synoptic meteorology in the south-east Pacific during the observations campaign VOCALS-REx in austral Spring 2008

We present a descriptive overview of the meteorology in the south eastern subtropical Pacific (SEP) during the VOCALS-REx intensive observations campaign which was carried out between October and November 2008. Mainly based on data from operational analyses, forecasts, reanalysis, and satellite observations, we focus on spatio-temporal scales from synoptic to planetary. A climatological context is given within which the specific conditions observed during the campaign are placed, with particular reference to the relationships between the large-scale and the regional circulations. The mean circulations associated with the diurnal breeze systems are also discussed. We then provide a summary of the day-to-day synoptic-scale circulation, air-parcel trajectories, and cloud cover in the SEP during VOCALS-REx. Three meteorologically distinct periods of time are identified and the large-scale causes for their different character are discussed. The first period was characterised by significant variability associated with synoptic-scale systems interesting the SEP; while the two subsequent phases were affected by planetary-scale disturbances with a slower evolution. The changes between initial and later periods can be partly explained from the regular march of the annual cycle, but contributions from subseasonal variability and its teleconnections were important. Across the whole of the two months under consideration we find a significant correlation between the depth of the inversion-capped marine boundary layer (MBL) and the amount of low cloud in the area of study. We discuss this correlation and argue that at least as a crude approximation a typical scaling may be applied relating MBL and cloud properties with the large-scale parameters of SSTs and tropospheric temperatures. These results are consistent with previously found empirical relationships involving lower-tropospheric stability.