Large Systematic Deviations Research Articles

Molecular and electrostatic origins of mixed salt partitioning phenomena in uncharged poly(ethylene oxide)-based membranes

Despite the increasing interest in membranes for water purification and resource recovery from aqueous electrolyte mixtures, few studies rigorously investigate the influence of salt solution composition (e.g., mole fraction and total salt concentration) on membrane material properties such as partition coefficients. Here, we systematically investigate the influence of solution composition on the partitioning of ionic species from binary aqueous salt solutions into crosslinked poly(ethylene glycol) diacrylate membranes at fixed ionic strength. These results are compared to partition coefficients observed for pure salt solutions. We observe large systematic deviations between the pure salt and mixed salt ion partition coefficients, indicating that the single salt partition coefficients that are often reported do not describe the more complex and realistic mixed salt scenario. Free energy calculations from molecular dynamics simulations, coupled with equilibrium thermodynamic modeling, indicate that mixed salt partitioning trends result from (i) different ions exhibiting different affinities for the membrane and (ii) the constraint of global electrical neutrality within the membrane. With this physical insight, we develop a simple approach to predicting the concentration of various ions in a membrane equilibrated with a mixed salt solution which requires no adjustable parameters.

Either Accurate Singlet-Triplet Gaps or Excited-State Structures: Testing and Understanding the Performance of TD-DFT for TADF Emitters.

The energy gap between the lowest singlet and triplet excited states (ΔEST) is a key property of thermally activated delayed fluorescence (TADF) emitters, where these states are dominated by charge-transfer (CT) character. Despite its well-known shortcomings concerning CT states, time-dependent density functional theory (TD-DFT) is widely used to predict this gap and study TADF. Moreover, polar CT states exhibit a strong interaction with their molecular environment, which further complicates their computational description. Addressing these two major challenges, this work studies the performance of Tamm-Dancoff-approximated TD-DFT (TDA-DFT) on the recent STGABS27 benchmark set,1 exploring different strategies to include orbital and structural relaxation, as well as dielectric embedding. The results show that the best-performing strategy is to calculate ΔEST at the ground-state structure using functionals with a surprisingly small amount of Fock exchange of ≈10% and without a (complete) solvent model. However, as this approach heavily relies on error cancellation to mimic dielectric relaxation, it is not robust and exhibits large systematic deviations in excited state energies, state characters, and structures. More rigorous approaches, including state-specific solvation, do not share these systematic deviations, but their predicted ΔEST values exhibit larger statistical errors. We thus conclude that for the description of CT states in dielectric environments, none of the tested TDA-DFT methods is competitive with the recently presented ROKS/PCM approach regarding robustness, accuracy, and computational efficiency.

PO15: Systematic Dwell Position Deviation of Elekta MR Compatible HDR Ring Applicators

<h3>Purpose</h3> (1) To identify a systematic dwell position deviation of Elekta MR compatible HDR ring applicators due to its design and (2) to demonstrate the dosimetric impact of the deviation. <h3>Materials and Methods</h3> In these ring applicators, the source is designed to travel precisely along the central axis of the ring tube. However, the actual source positions deviate from the central axis due to the semi-rigid design of the wire carrying the source. To quantify the deviation, in-house QA devices were built using decommissioned ring applicators of three different diameters (26mm, 30mm, and 34mm). The ring applicators were modified by replacing their top caps with a 1 mm thick transparent plastic plate. This allowed proper visualization of both the vendor-provided wire QA markers and the actual Ir-192 source. The high-resolution camera of the Elekta Flexitron system was used to acquire images of the applicator and the source. The source was driven to dwell positions with a 5 mm increment to cover the full visible range of the ring. An image was acquired at each dwell position. This procedure was repeated 5 times for each ring size. Two observers independently measured the arc length traveled by the source from the first dwell position to other dwell positions. The deviation was calculated as the difference between the measured arc length and the intended dwell position (converted to arc length). <h3>Results</h3> The deviation was found to be a function of the arc distance from the first dwell position. It increases almost linearly with arc length, experiences a sharp increase before settling in a range between 5 mm and 6 mm. Up to 6 mm deviation was found for ring applicators of all three different diameters. Although there were small interobserver differences (mean = 0.1 mm, SD = 0.13 mm), the results were highly reproducible (SD = 0.09 mm). The dwell position deviations result in remarkable differences of the isodose curves surrounding the ring applicator. The measured deviations were applied to our library plan for cervical cancer using 30 mm ring and 60 mm tandem. The isodose lines in the plane of the ring before and after the offsets were applied are shown in figure 1(a) and (b), respectively. <h3>Conclusions</h3> Large systematic dwell positions deviations of the Elekta MR compatible HDR ring applicators has been quantified. These deviations may have significant dosimetric impact on HDR treatment. Therefore, they should be considered by the treatment planning system for more accurate dose computations.

Activity coefficients of aqueous electrolytes from implicit-water molecular dynamics simulations.

We obtain activity coefficients in NaCl and KCl solutions from implicit-water molecular dynamics simulations, at 298.15K and 1bar, using two distinct approaches. In the first approach, we consider ions in a continuum with constant relative permittivity (ɛr) equal to that of pure water; in the other approach, we take into account the concentration-dependence of ɛr, as obtained from explicit-water simulations. Individual ion activity coefficients (IIACs) are calculated using gradual insertion of single ions with uniform neutralizing backgrounds to ensure electroneutrality. Mean ionic activity coefficients (MIACs) obtained from the corresponding IIACs in simulations with constant ɛr show reasonable agreement with experimental data for both salts. Surprisingly, large systematic negative deviations are observed for both IIACs and MIACs in simulations with concentration-dependent ɛr. Our results suggest that the absence of hydration structure in implicit-water simulations cannot be compensated by correcting for the concentration-dependence of the relative permittivity ɛr. Moreover, even in simulations with constant ɛr for which the calculated MIACs are reasonable, the relative positioning of IIACs of anions and cations is incorrect for NaCl. We conclude that there are severe inherent limitations associated with implicit-water simulations in providing accurate activities of aqueous electrolytes, a finding with direct relevance to the development of electrolyte theories and to the use and interpretation of implicit-solvent simulations.

Screening Deep Eutectic Solvents for CO2 Capture With COSMO-RS.

In this work, 502 experimental data for CO2 solubilities and 132 for Henry's constants of CO2 in DESs were comprehensively summarized from literatures and used for further verification and development of COSMO-RS. Large systematic deviations of 62. 2, 59.6, 63.0, and 59.1% for the logarithmic CO2 solubilities in the DESs (1:2, 1:3, 1:4, 1:5), respectively, were observed for the prediction with the original COSMO-RS, while the predicted Henry's constants of CO2 in the DESs (1:1.5, 1:2, 1:3, 1:4, 1:5) at temperatures ranging of 293.15–333.15 K are more accurate than the predicted CO2 solubility with the original COSMO-RS. To improve the performance of COSMO-RS, 502 data points of CO2 solubility in the DESs (1:2, 1:3, 1:4, 1:5) were used for correcting COSMO-RS with a temperature-pressure dependent parameter, and the CO2 solubility in the DES (1:6) was predicted to further verify the performance of the corrected model. The results indicate that the corrected COSMO-RS can significantly improve the model performance with the ARDs decreasing down to 6.5, 4.8, 6.5, and 4.5% for the DESs (1:2, 1:3, 1:4, and 1:5), respectively, and the corrected COSMO-RS with the universal parameters can be used to predict the CO2 solubility in DESs with different mole ratios, for example, for the DES (1:6), the corrected COSMO-RS significantly improves the prediction with an ARD of 10.3% that is much lower than 78.2% provided by the original COSMO-RS. Additionally, the result from COSMO-RS shows that the σ-profiles can reflect the strength of molecular interactions between an HBA (or HBD) and CO2, determining the CO2 solubility, and the dominant interactions for CO2 capture in DESs are the H-bond and Van der Waals force, followed by the misfit based on the analysis of the predicted excess enthalpies.

Changing the influence of the egocentric reference frame impacts deviations in haptic parallelity matching

The large systematic deviations in haptic parallelity matching are most likely due to the biasing influence of the hand-centered egocentric reference frame. Previous results showed that eliminating or reducing this bias resulted in smaller deviations, with significantly larger effects observed in female participants. The current study investigated the effect of reducing the egocentric bias in a pure haptic condition. Blind-folded male and female participants had to feel the orientation of a reference bar with their non-dominant hand and to parallel this orientation on a test bar with their dominant hand. In one condition, they were instructed to use their flat-stretched hand to feel and match the bars, while in the other condition (HPF), they were instructed to set the test bar while gripping the bar with the fingers and thumb. It was hypothesized that the latter would reduce the biasing influence of the hand-centered egocentric reference frame. Results showed that this was indeed the case. Deviations were significantly smaller for HPF; however, this effect was the same in both genders. The previously observed gender effect, showing a significantly larger improvement for women when reducing the influence of the egocentric reference frame, was not replicated.

Sensitivity analysis of the WATER9 model: emissions of odorous compounds from passive liquid surfaces present in wastewater treatment plants

Empirical mathematical models have been frequently used to estimate emissions and to act in the prevention of possible impacts from odorous compounds. Based on the regulatory WATER9 model, the present study had the aim to evaluate the deviations originating from the simplification of using the effective diameter (in contrast to the conceptually appropriate use of the linear physical fetch) as fetch parameter in the calculation of the global mass transfer coefficient at passive liquid surfaces at wastewater treatment plants (WWTPs). The present analysis incorporated the influence of different values of wind velocity, molecular diffusivity and Henry's Law constant. The analyses for the calculation of the mass transfer coefficients were developed for 1,000 wind speeds, chosen using the Monte Carlo method, three WWTPs and three compounds of environmental relevance, spanning different behaviour regarding their volatilisation. The wind speed had a direct influence on the deviations for all types of compounds analysed. However, this parameter was found to be more representative for the compounds whose volatilisation is limited by conditions in the liquid phase. Furthermore, the deviations for the calculation of the mass transfer coefficient arising from the use of the effective diameter as fetch parameter were significantly larger for liquid phase-dominated compounds, compared to gas phase-dominated compounds. Comparison against available experimental data confirm that the use of the effective diameter as the fetch parameter makes the model predictions further depart from the experimental values. The present analysis shows that, for a varied range of wind speed and WWTP configurations, the use of the actual physical fetch shall be preferred over the use of the effective diameter in emission models for WWTPs, so as to avoid the introduction of potentially large systematic deviations.

Two-Component Structure of the Radio Source 0014+813 from VLBI Observations within the CONT14 Program

We consider a method of reconstructing the structure delay of extended radio sources without constructing their radio images. The residuals derived after the adjustment of geodetic VLBI observations are used for this purpose. We show that the simplest model of a radio source consisting of two point components can be represented by four parameters (the angular separation of the components, the mutual orientation relative to the poleward direction, the flux-density ratio, and the spectral index difference) that are determined for each baseline of a multi-baseline VLBI network. The efficiency of this approach is demonstrated by estimating the coordinates of the radio source 0014+813 observed during the two-week CONT14 program organized by the International VLBI Service (IVS) in May 2014. Large systematic deviations have been detected in the residuals of the observations for the radio source 0014+813. The averaged characteristics of the radio structure of 0014+813 at a frequency of 8.4 GHz can be calculated from these deviations. Our modeling using four parameters has confirmed that the source consists of two components at an angular separation of ~0.5 mas in the north–south direction. Using the structure delay when adjusting the CONT14 observations leads to a correction of the average declination estimate for the radio source 0014+813 by 0.070 mas.

Not a Copernican observer: biased peculiar velocity statistics in the local Universe

We assess the effect of the local large scale structure on the estimation of two-point statistics of the observed radial peculiar velocities of galaxies. A large N-body simulation is used to examine these statistics from the perspective of random observers as well as "Local Group (LG)-like" observers conditioned to reside in an environment resembling the observed universe within 20 Mpc. The local environment systematically distorts the shape and amplitude of velocity statistics with respect to ensemble-averaged measurements made by a Copernican (random) observer. The Virgo cluster has the most significant impact, introducing large systematic deviations in all the statistics. For a simple "top-hat" selection function, an idealized survey extending to $\sim 160h^{-1}\,{\rm Mpc}$ or deeper is needed to completely mitigate the effects of the local environment. Using shallower catalogues leads to systematic deviations of the order of $50$ to $200\%$ depending on the scale considered. For a flat redshift distribution similar to the one of the CosmicFlows-3 survey, the deviations are even more prominent in both the shape and amplitude at all separations considered $({\stackrel{<}{{}_\sim}} 100h^{-1}\,{\rm Mpc})$. Conclusions based on statistics calculated without taking into account the impact of the local environment should be revisited.

Are optical distortions used as a cue for material properties of thick transparent objects?

Fleming, Jäkel, and Maloney (2011) asked subjects to match perceived material properties of thick, clear transparent objects in photo-realistic scenes by adjusting the refractive index. They found approximate correspondence between standard and test objects but also large systematic deviations. Nevertheless, they concluded that estimated refraction is used as an indicator for material properties of light-transmitting objects and emphasized the role of object-induced background distortions in this process. This, however, seems not plausible, because the necessary information for inferring the refractive index from distortions-for example, the object's exact shape and thickness, its background distance, and the undistorted background-was not available in their situation. A more plausible alternative explanation is that the subjects did not match estimated refractive indices, but instead performed simple similarity matches based directly on image attributes related to background distortions or specular reflections. We tested this hypothesis in a similar matching experiment in which it was possible to predict the refractive index for a similarity match based on background distortions and for a similarity match based on specular reflections. Our subjects always chose a value between these two predictions. The specular reflection tends to be the dominant factor as soon as it becomes clearly noticeable. Our findings are compatible with the assumption that the subjects tried to find a compromise between two image-based similarity criteria. They do not seem to be consistent with the assumption that the matches are made on the basis of internal estimates of refractive indices.

ELUCID—EXPLORING THE LOCAL UNIVERSE WITH THE RECONSTRUCTED INITIAL DENSITY FIELD. I. HAMILTONIAN MARKOV CHAIN MONTE CARLO METHOD WITH PARTICLE MESH DYNAMICS

Simulating the evolution of the local universe is important for studying galaxies and the intergalactic medium in a way free of cosmic variance. Here we present a method to reconstruct the initial linear density field from an input non-linear density field, employing the Hamiltonian Markov Chain Monte Carlo (HMC) algorithm combined with Particle Mesh (PM) dynamics. The HMC+PM method is applied to cosmological simulations, and the reconstructed linear density fields are then evolved to the present day with N-body simulations. The constrained simulations so obtained accurately reproduce both the amplitudes and phases of the input simulations at various $z$. Using a PM model with a grid cell size of 0.75 Mpc/h and 40 time-steps in the HMC can recover more than half of the phase information down to a scale k~0.85 h/Mpc at high z and to k~3.4 h/Mpc at z=0, which represents a significant improvement over similar reconstruction models in the literature, and indicates that our model can reconstruct the formation histories of cosmic structures over a large dynamical range. Adopting PM models with higher spatial and temporal resolutions yields even better reconstructions, suggesting that our method is limited more by the availability of computer resource than by principle. Dynamic models of structure evolution adopted in many earlier investigations can induce non-Gaussianity in the reconstructed linear density field, which in turn can cause large systematic deviations in the predicted halo mass function. Such deviations are greatly reduced or absent in our reconstruction.

Illusory rotation in the haptic perception of a moving bar

Haptic matching of the orientation of bars separated by a horizontal distance leads to large systematic deviations. This finding leads to the following intriguing question which we investigated in this study: How will a bar moving from left to right in a fixed orientation be perceived by blindfolded observers? Interestingly, this previous finding predicts that the translating bar will cause the illusory perception of a rotation. In our experiment, we used psychophysical methods to determine the rotation needed to perceive the bar as non-rotating, for both rightward and leftward translations. From our results, it can be estimated that, on average, a bar translating in parallel over 60cm is perceived as rotating 18°, so we established that the predicted illusory rotation indeed exists. This implies that static and dynamic signals are processed in a similar way.

Mass measurements near ther-process path using the Canadian Penning Trap mass spectrometer

The masses of 40 neutron-rich nuclides from $Z=51$ to 64 were measured at an average precision of $\ensuremath{\delta}m/m={10}^{\ensuremath{-}7}$ using the Canadian Penning Trap mass spectrometer at Argonne National Laboratory. The measurements, of fission fragments from a ${}^{252}$Cf spontaneous fission source in a helium gas catcher, approach the predicted path of the astrophysical $r$ process. Where overlap exists, this data set is largely consistent with previous measurements from Penning traps, storage rings, and reaction energetics, but large systematic deviations are apparent in $\ensuremath{\beta}$-endpoint measurements. Differences in mass excess from the 2003 Atomic Mass Evaluation of up to 400 keV are seen, as well as systematic disagreement with various mass models.

Inter-observer variability in contouring the penile bulb on CT images for prostate cancer treatment planning.

Several investigations have recently suggested the existence of a correlation between the dose received by the penile bulb (PB) and the risk of erectile dysfunction (ED) after radical radiotherapy for clinically localized prostate carcinoma.A prospective multi-Institute study (DUE-01) was implemented with the aim to assess the predictive parameters of ED. Previously, an evaluation of inter-observer variations of PB contouring was mandatory in order to quantify its impact on PB dose-volume parameters by means of a dummy run exercise.Fifteen observers, from different Institutes, drew the PB on the planning CT images of ten patients; inter-observer variations were analysed in terms of PB volume variation and cranial/caudal limits. 3DCRT treatment plans were simulated to evaluate the impact of PB contouring inter-variability on dose-volume statistics parameters. For DVH analysis the values of PB mean dose and the volume of PB receiving more than 50 Gy and 70 Gy (V50 and V70, respectively) were considered. Systematic differences from the average values were assessed by the Wilcoxon test.Seven observers systematically overestimated or underestimated the PB volume with deviations from the average volumes ranging between -48% and +34% (p < 0.05). The analysis of the cranial and caudal borders showed a prevalence of random over systematic deviations.Inter-observer contouring variability strongly impacts on DVH parameters, although standard deviations of inter-patient differences were larger than inter-observer variations: 14.5 Gy versus 6.8 Gy for mean PB dose, 23.0% versus 11.0% and 16.8% versus 9.3% for V50 and V70 respectively.In conclusion, despite the large inter-observer variation in contouring PB, a large multi-centric study may have the possibility to detect a possible correlation between PB % dose-volume parameters and ED. The impact of contouring uncertainty could be reduced by "a posteriori" contouring from a single observer or by introducing Magnetic Resonance Imaging (MRI) in the planning procedures and/or in improving the skill of observers through post-dummy run tutoring of those observers showing large systematic deviations from the mean.

The material-size illusion - The influence of material properties on haptic perception of volume

Haptic matching of the orientation of bars separated by a horizontal distance leads to large systematic deviations (eg Kappers and Koenderink, 1999 Perception 28 781–795). A bar on the right side has to be rotated clockwise in order to be perceived as parallel to a bar at the left side. This finding leads to the following intriguing question which we investigated in this study: Will a bar moving from left to right in a fixed orientation be perceived as rotating counterclockwise? Blindfolded subjects had to touch a bar that moved from left to right or from right to left while it was rotating clockwise or counterclockwise with di erent speeds or did not rotate. For each trial they had to decide whether the rotation was clockwise or counterclockwise. From psychometric curves fitted to the data, we could determine that the results were consistent with the findings in the static case: A bar moving from left to right has to rotate clockwise in order to be perceived as non-rotating (and vice versa). In other words, a translating bar causes the illusory perception of a rotation.

Differential effects of non-informative vision and visual interference on haptic spatial processing

The primary purpose of this study was to examine the effects of non-informative vision and visual interference upon haptic spatial processing, which supposedly derives from an interaction between an allocentric and egocentric reference frame. To this end, a haptic parallelity task served as baseline to determine the participant-dependent biasing influence of the egocentric reference frame. As expected, large systematic participant-dependent deviations from veridicality were observed. In the second experiment we probed the effect of non-informative vision on the egocentric bias. Moreover, orienting mechanisms (gazing directions) were studied with respect to the presentation of haptic information in a specific hemispace. Non-informative vision proved to have a beneficial effect on haptic spatial processing. No effect of gazing direction or hemispace was observed. In the third experiment we investigated the effect of simultaneously presented interfering visual information on the haptic bias. Interfering visual information parametrically influenced haptic performance. The interplay of reference frames that subserves haptic spatial processing was found to be related to both the effects of non-informative vision and visual interference. These results suggest that spatial representations are influenced by direct cross-modal interactions; inter-participant differences in the haptic modality resulted in differential effects of the visual modality.

Allocentric and egocentric reference frames in the processing of three-dimensional haptic space.

The main goal of our study is to gain insight into the reference frames involved in three-dimensional haptic spatial processing. Previous research has shown that two-dimensional haptic spatial processing is prone to large systematic deviations. A weighted average model that identifies the origin of the systematic error patterns in the biasing influence of an egocentric reference frame on the allocentric reference frame was proposed as an explanation of the results. The basis of the egocentric reference frame was linked either to the hand or to the body. In the present study participants had to construct a field of parallel bars that could be oriented in three dimensions. First, systematic error patterns were found also in this three-dimensional haptic parallelity task. Second, among the different models tested for their accuracy in explaining the error patterns, the Hand-centered weighted average model proved to most closely resemble the data. A participant-specific weighting factor determined the biasing influence of the hand-centered egocentric reference frame. A shift from the allocentric towards the egocentric frame of reference of approximately 20% was observed. These results support the hypothesis that haptic spatial processing is a product of the interplay of diverse, but synergistically operating frames of reference.

Electronic spectroscopy of jet-cooled HCP+: Molecular structure, phosphorus hyperfine structure, and Renner-Teller analysis

Laser-induced fluorescence spectra of jet-cooled HCP(+) and DCP(+) have been obtained with the pulsed discharge technique using HCPDCP and argon precursor mixtures. Transitions involving all of the excited state vibrations have been observed and a set of vibrational constants has been obtained. High-resolution spectra of the (2)Pi(32) components of the 0(0) (0) bands of both isotopomers have been recorded, and these spectra show resolved phosphorus hyperfine structure which allowed the determination of the excited state Fermi contact parameter. The B values were used to obtain the ground and excited state effective geometric parameters as r(0) (")(CH)=1.077(2) A, r(0) (")(CP)=1.6013(3) A, r(0) (')(CH)=1.082(2) A, and r(0) (')(CP)=1.5331(3) A. A Renner-Teller analysis of the ground state vibrational energy levels obtained from the literature was attempted. All of the observed levels of DCP(+) and the majority of those of HCP(+) were satisfactorily fitted with a standard Renner-Teller model, but three HCP(+) levels showed large systematic deviations which could not be accommodated by reassignments or improvements in the Fermi resonance Hamiltonian. Further improvements in the theory or in the experimental data will be needed to resolve this discrepancy.

Effects of Context on a Visual 3-D Pointing Task

We examined the effects of egocentric and contextual references on a 3-D exocentric pointing task. Large systematic deviations were found for the slant (angle in the horizontal plane). For most observers, the deviations were smaller when the veridical pointing direction was parallel to a wall. For some observers the size of the deviations was also dependent on whether the veridical pointing direction was frontoparallel or not. For the tilt (angle in the vertical plane), the deviations were smaller and less systematic. Hence, although observers show comparable systematic deviations, the way in which the presence of structure in an environment is used for judging positions of objects is observer-dependent.

Visual space under free viewing conditions

Most research on visual space has been done under restricted viewing conditions and in reduced environments. In our experiments, observers performed an exocentric pointing task, a collinearity task, and a parallelity task in a entirely visible room. We varied the relative distances between the objects and the observer and the separation angle between the two objects. We were able to compare our data directly with data from experiments in an environment with less monocular depth information present. We expected that in a richer environment and under less restrictive viewing conditions, the settings would deviate less from the veridical settings. However, large systematic deviations from veridical settings were found for all three tasks. The structure of these deviations was task dependent, and the structure and the deviations themselves were comparable to those obtained under more restricted circumstances. Thus, the additional information was not used effectively by the observers.