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At least 1,261 records · Page 70

A Consistent Representation of Cloud Overlap and Cloud Subgrid Vertical Heterogeneity

Many global climate models underestimate the cloud cover and overestimate the cloud albedo, especially for low-level clouds. We determine how a correct representation of the vertical structure of clouds can fix part of this bias. We use the 1D McICA framework and focus on low-level clouds. Using Large Eddy Simulations results as reference, we propose a method based on exponential-random overlap that represents the cloud overlap between layers and the subgrid cloud properties over several vertical scales, with a single value of the overlap parameter. Starting from a coarse vertical grid, representative of atmospheric models, this algorithm is used to generate the vertical profile of the cloud fraction with a finer vertical resolution, or to generate it on the coarse grid but with subgrid heterogeneity and cloud overlap that ensures a correct cloud cover. Doing so we find decorrelation lengths are dependent on the vertical resolution, except if the vertical subgrid heterogeneity and interlayer overlap are taken into account coherently. We confirm that the frequently used maximum-random overlap leads to a significant error by underestimating the low-level cloud cover with a relative error of about 50%, that can lead to an error of SW cloud albedo as big as 70%. Not taking into account the subgrid vertical heterogeneity of clouds can cause a relative error of 20% in brightness, assuming the cloud cover is correct.

54 ENVIRONMENTAL SCIENCES↗

ON THE ACCURACY OF THE DIFFERENTIAL EMISSION MEASURE DIAGNOSTICS OF SOLAR PLASMAS. APPLICATION TO SDO/AIA. I. ISOTHERMAL PLASMAS

Differential emission measure (DEM) analysis is a major diagnostic tool for stellar atmospheres. However, both its derivation and its interpretation are notably difficult because of random and systematic errors, and the inverse nature of the problem. We use simulations with simple thermal distributions to investigate the inversion properties of SDO/AIA observations of the solar corona. This allows a systematic exploration of the parameter space, and using a statistical approach the respective probabilities of all the DEMs compatible with the uncertainties can be computed. Following this methodology, several important properties of the DEM inversion, including new limitations, can be derived and presented in a very synthetic fashion. In this first paper, we describe the formalism and we focus on isothermal plasmas as building blocks to understand the more complex DEMs studied in the second paper. The behavior of the inversion of AIA data being thus quantified, and we provide new tools to properly interpret the DEM. We quantify the improvement of the isothermal inversion with six AIA bands compared to previous EUV imagers. The maximum temperature resolution of AIA is found to be 0.03 log T{sub e} , and we derive a rigorous test to quantify the compatibility of observations with the isothermal hypothesis. However, we demonstrate limitations in the ability of AIA alone to distinguish different physical conditions.

79 ASTRONOMY AND ASTROPHYSICS↗

The Lyman α forest in optically thin hydrodynamical simulations

We study the statistics of the Lyα forest in a flat Λ cold dark matter cosmology with the N-body + Eulerian hydrodynamics code NYX.We produce a suite of simulations, covering the observationally relevant redshift range 2 ≤ z ≤ 4. We find that a grid resolution of 20 h-1kpc is required to produce 1 per cent convergence of Lyα forest flux statistics, up to k = 10 h -1 Mpc. In addition to establishing resolution requirements, we study the effects of missing modes in these simulations, and find that box sizes of L > 40h -1 Mpc are needed to suppress numerical errors to a sub-per cent level. Our optically thin simulations with the ionizing background prescription of Haardt & Madau reproduce an intergalactic medium density-temperature relation with T 0 ≈ 10 4 K and γ ≈ 1.55 at z = 2, with a mean transmitted flux close to the observed values. When using the ionizing background prescription of Faucher-Giguère et al., the mean flux is 10-15 per cent below observed values at z = 2, and a factor of 2 too small at z = 4. We show the effects of the common practice of rescaling optical depths to the observed mean flux and how it affects convergence rates. We also investigate the practice of 'splicing' results from a number of different simulations to estimate the 1D flux power spectrum and show it is accurate at the 10 per cent level. Finally, we find that collisional heating of the gas from dark matter particles is negligible in modern cosmological simulations.

79 ASTRONOMY AND ASTROPHYSICS↗

Extracting Topological Orders of Generalized Pauli Stabilizer Codes in Two Dimensions

In this paper, we introduce an algorithm for extracting topological data from translation invariant generalized Pauli stabilizer codes in two-dimensional systems, focusing on the analysis of anyon excitations and string operators. The algorithm applies to Z d qudits, including instances where d is a nonprime number. This capability allows the identification of topological orders that differ from the Z d toric codes. It extends our understanding beyond the established theorem that Pauli stabilizer codes for Z p qudits (with p being a prime) are equivalent to finite copies of Z p toric codes and trivial stabilizers. The algorithm is designed to determine all anyons and their string operators, enabling the computation of their fusion rules, topological spins, and braiding statistics. The method converts the identification of topological orders into computational tasks, including Gaussian elimination, the Hermite normal form, and the Smith normal form of truncated Laurent polynomials. Furthermore, the algorithm provides a systematic approach for studying quantum error-correcting codes. We apply it to various codes, such as self-dual CSS quantum codes modified from the two-dimensional honeycomb color code and non-CSS quantum codes that contain the double semion topological order or the six-semion topological order. Published by the American Physical Society 2024

Physics↗

Sci-Fri PM: Radiation Therapy, Planning, Imaging, and Special Techniques - 09: Impact of the distance of reflective markers from linac isocenter on the positional accuracy of an infrared tracking system

Purpose: The HexaPOD™ six degree of freedom couchtop is equipped with an optical tracking system, consisting of a stereoscopic camera and a reference frame (RF) carrying infrared reflective markers. The manufacturer recommends placing the RF within 50 cm from linac isocenter (ISO), which is a serious limitation since the RF does not fit around the shoulders of most brain patients. This study quantifies the impact of extended RF distances from ISO on positional accuracy. Methods: An in-house tool with an estimated resolution of 0.3 mm and 0.1° was used. It is a large cube and a mathematical model of HexaPOD motion to determine the intersection of room lasers with the ruled cube edges. Combinations of translations (±1 and ±3 cm) and rotations (±2.5°) were executed on two HexaPOD couchtops for multiple RF distances from ISO (35 to 77 cm). For each combination, ten laser readings were fed into a least squares algorithm to determine the executed translations and rotations while minimizing operator reading errors. Results: The usable tracking volume is up to an RF distance of 82 cm from ISO. Positional accuracy of the HexaPOD/iGuide system is 0.6 mm and 0.1° (95% confidence). Positional accuracy variations versus RF distance from ISO are statistically insignificant (p = 0.05). Our results generally confirm recent internal estimates by the manufacturer (for future release). Conclusions: RF distances up to 77 cm from ISO are clinically acceptable, provided performing a patient safety study with a verification scan.

60 APPLIED LIFE SCIENCES↗

One-to-one aeroservoelastic validation of operational loads and performance of a 2.8 MW wind turbine model in OpenFAST

Abstract. This article presents a validation study of the popular aeroservoelastic code suite OpenFAST leveraging weeks of measurements obtained during normal operation of a 2.8 MW land-based wind turbine. Measured wind conditions were used to generate one-to-one turbulent flow fields (i.e., comparing simulation to measurement in 10 min increments, or bins) through unconstrained and constrained assimilation methods using the kinematic turbulence generators TurbSim and PyConTurb. A total of 253 bins of 10 min of normal turbine operation were selected for analysis, and a statistical comparison in terms of performance and loads is presented. We show that successful validation of the model was not strongly dependent on the type of inflow assimilation method used for mean quantities of interest, which had median modeling errors per wind-speed interval generally within 5 %–10 % of the measurement. The type of inflow assimilation method did have a larger effect on the fatigue predictions for blade-root flapwise and tower-base fore–aft quantities, which surprisingly saw larger errors from the assumed higher-fidelity assimilation methods. Avenues for further work are discussed and include possible improvements to the aerodynamic, structural, and controller modeling that may offer insight on the origin of the up to ∼ 40 % median overprediction of fatigue for these quantities.

17 WIND ENERGY↗

Statistical Tool Size Study for Computer-Controlled Optical Surfacing

Over the past few decades, computer-controlled optical surfacing (CCOS) systems have become more deterministic. A target surface profile can be predictably achieved with a combination of tools of different sizes. However, deciding the optimal set of tool sizes that will achieve the target residual error in the shortest run time is difficult, and no general guidance has been proposed in the literature. In this paper, we present a computer-assisted study on choosing the proper tool size for a given surface error map. First, we propose that the characteristic frequency ratio (CFR) can be used as a general measure of the correction capability of a tool over a surface map. Second, the performance of different CFRs is quantitatively studied with a computer simulation by applying them to guide the tool size selection for polishing a large number of randomly generated surface maps with similar initial spatial frequencies and root mean square errors. Finally, we find that CFR = 0.75 achieves the most stable trade-off between the total run time and the number of iterations and thus can be used as a general criterion in tool size selection for CCOS processes. To the best of our knowledge, the CFR is the first criterion that ties tool size selection to overall efficiency.

36 MATERIALS SCIENCE↗

Impact of numerics on the predictive capabilities of reacting flow LES

Combustors in modern aerospace propulsion systems are highly optimized devices and further enhancements to their performance will require advanced predictive modeling techniques. The LES approach has potential to be such a technique, but demonstration of its true predictive capability remains a challenge. In this paper, a methodical study is performed to assess the impact of numerical error on the predictive capabilities of LES and to distinguish it from error arising from physical modeling. Four codes are employed to simulate the bluff body stabilized flame experiment of Volvo Flygmotor AB. The physical models (governing equations and sub-grid models) are kept identical between the codes so that the physical modeling error is the same. For the same reason, computational grids are also kept identical since the sub-grid models are grid dependent. Results indicate that all codes produce a very similar solution for the non-reacting flow in terms of large scale unsteady vortex shedding behavior, mean profiles and second order turbulence statistics, on a suitably refined grid. This solution is also very close to the experimentally observed behavior of the flow. In contrast, for the reacting case, solutions from the various codes exhibit significant differences when analyzed under the same metrics and with similar or even finer grid resolution than that used for the non-reacting case. These differences are large enough to change the macroscopic behavior of the flow, e.g. some codes predict symmetric vortex shedding while others predict asymmetric shedding and some codes show strong recirculation zones while others show stagnant regions behind the bluff body. It is also shown that none of the solutions truly predicts the experimentally observed flow. Given that the physical sub-grid models and computational grids are the same in all the simulations, the inconsistency between results points to a significant impact of numerical methods and, hence, numerical error. The need for mitigation of this impact is highlighted, along with the need for metrics detailing how LES should be applied to reacting flows. It is suggested that both of these issues should be the focus of future work.

Energy & Fuels↗

SPIDER. V. MEASURING SYSTEMATIC EFFECTS IN EARLY-TYPE GALAXY STELLAR MASSES FROM PHOTOMETRIC SPECTRAL ENERGY DISTRIBUTION FITTING

We present robust statistical estimates of the accuracy of early-type galaxy stellar masses derived from spectral energy distribution (SED) fitting as functions of various empirical and theoretical assumptions. Using large samples consisting of {approx}40,000 galaxies from the Sloan Digital Sky Survey (SDSS; ugriz), of which {approx}5000 are also in the UKIRT Infrared Deep Sky Survey (YJHK), with spectroscopic redshifts in the range 0.05 {<=} z {<=} 0.095, we test the reliability of some commonly used stellar population models and extinction laws for computing stellar masses. Spectroscopic ages (t), metallicities (Z), and extinctions (A{sub V} ) are also computed from fits to SDSS spectra using various population models. These external constraints are used in additional tests to estimate the systematic errors in the stellar masses derived from SED fitting, where t, Z, and A{sub V} are typically left as free parameters. We find reasonable agreement in mass estimates among stellar population models, with variation of the initial mass function and extinction law yielding systematic biases on the mass of nearly a factor of two, in agreement with other studies. Removing the near-infrared bands changes the statistical bias in mass by only {approx}0.06 dex, adding uncertainties of {approx}0.1 dex at the 95% CL. In contrast, we find that removing an ultraviolet band is more critical, introducing 2{sigma} uncertainties of {approx}0.15 dex. Finally, we find that the stellar masses are less affected by the absence of metallicity and/or dust extinction knowledge. However, there is a definite systematic offset in the mass estimate when the stellar population age is unknown, up to a factor of 2.5 for very old (12 Gyr) stellar populations. We present the stellar masses for our sample, corrected for the measured systematic biases due to photometrically determined ages, finding that age errors produce lower stellar masses by {approx}0.15 dex, with errors of {approx}0.02 dex at the 95% CL for the median stellar age subsample.

79 ASTRONOMY AND ASTROPHYSICS↗

A Refined Global Segmentation of X-Ray CT Images for Multi-phase Geomaterials

X-ray computed tomography images of three-phase silica sand and glass bead specimens are analyzed and used to evaluate the segmentation performances of Otsu-, and recursion-based multilevel algorithms. A global image segmentation technique that combines iterative and recursive algorithms, namely a refined statistics-based global segmentation is proposed for segmenting multi-phase granular geomaterials. The performance of the proposed algorithm is tested by segmenting partially saturated silica sand and glass bead specimens. For the tested silica sand specimen, the refined statistics method estimated void ratio and degree of saturation were 0.67 and 39.35%. The estimates for the glass bead specimen yielded 0.64 and 43.49%, respectively. The true void ratio (0.66) and degree of saturation (37.71%) were determined with a user-controlled Image processing software package—Image-Pro. It was found that the proposed method estimated the void ratio and the degree of saturation with 1.52 and 4.35 percent errors for the silica sand and with 15.63 and 0.34 percent errors for the glass bead, respectively. The computational time of the proposed method was found to be shorter than other methods considered. Overall, it is concluded that the proposed technique performed better in segmenting three-phase granular geomaterials.

42 ENGINEERING↗

Constraining gravity with a new precision 𝐸 𝐺 estimator using Planck + SDSS BOSS data

The 𝐸 𝐺 statistic is a discriminating probe of gravity developed to test the prediction of general relativity (GR) for the relation between gravitational potential and clustering on the largest scales in the observable Universe. We present a novel high-precision estimator for the 𝐸 𝐺 statistic using CMB lensing and galaxy clustering correlations that carefully matches the effective redshifts across the different measurement components to minimize corrections. A suite of detailed tests is performed to characterize the estimator’s accuracy, its sensitivity to assumptions and analysis choices, and the non-Gaussianity of the estimator’s uncertainty is characterized. After finalization of the estimator, it is applied to Planck CMB lensing and SDSS CMASS and LOWZ galaxy data. We report the first harmonic space measurement of 𝐸 𝐺 using the LOWZ sample and CMB lensing and also updated constraints using the final CMASS sample and the latest Planck CMB lensing map. We find $\hat{𝐸}$$^{Planck+CMASS}_{𝐺}$ = 0.3⁢6$^{+0.06}_{−0.05}$⁢(68.27%) and $\hat{𝐸}$$^{Planck+LOWZ}_{𝐺}$ = 0.4⁢0$^{+0.11}_{−0.09}$⁢(68.27%), with additional subdominant systematic error budget estimates of 2% and 3%, respectively. Using Ω m,0 constraints from Planck and SDSS BAO observations, Λ⁢CDM-GR predicts 𝐸$^{GR}_ {𝐺}$⁡(𝑧 =0.555) = 0.401 ± 0.005 and 𝐸$^{GR}_{𝐺}$⁡(𝑧 =0.316) = 0.452 ± 0.005 at the effective redshifts of the CMASS and LOWZ based measurements. We report the measurement to be in good statistical agreement with the Λ⁢CDM-GR prediction and report that the measurement is also consistent with the more general GR prediction of scale independence for 𝐸 𝐺 . Furthermore, this work provides a carefully constructed and calibrated statistic with which 𝐸 𝐺 measurements can be confidently and accurately obtained with upcoming survey data.

79 ASTRONOMY AND ASTROPHYSICS↗

Comprehensive Performance Calibration Guidance for Perovskites and Other Emerging Solar Cells

Emerging photovoltaic (PV) technologies (e.g., organic, perovskite, and solution processed quantum dot) have attracted remarkable attention with the rapid growth of their efficiencies, and their transition toward commercialization. Accurate and reliable efficiency measurements of these PV technologies are crucial, yet much more complicated than for conventional PV technologies due to the former's pronounced dynamic responses to changes in measurement conditions (e.g., current–voltage (I–V) scan rate and preconditioning) and their susceptibility to degradation. Adjustments to the measurement procedures are therefore necessary so that a reproducible “steady state” is reached during measurement. Furthermore, given the small size of many emerging cells, inappropriate device area definition and solar simulator setup can lead to measurement errors. Here, comprehensive efficiency calibration guidance is offered for emerging solar cells, including area measurement; spectral irradiance translation to standard test conditions; and steady-state electrical performance. The necessity of reporting steady-state efficiency is justified with a statistical performance comparison between conventional and steady-state I–V scans over hundreds of cells the group has received globally for efficiency certifications. The procedures described here do not require specialized measurement instrumentation; what matters most are changes to the measurement protocols. These described changes aim to enable better comparisons between reported efficiencies.

14 SOLAR ENERGY↗

Global reconstructed daily surge levels from the 20th Century Reanalysis (1871–2010)

Studying the effect of global patterns of wind and pressure gradients on the sea level variation (storm surge) is a key issue in understanding the recent climate change effect on the dynamical state of the ocean. The analysis of the spatial and temporal variability of storm surges from observations is a difficult task to accomplish since observations are not homogeneous in time, scarce in space, and moreover, their temporal coverage is limited. A recent global surge database developed by AVISO (DAC, Dynamic Atmospheric Correction) fulfilled the lack of data in terms of spatial coverage, but not regarding time extent, since it only includes the last two decades (1992–2014). In this work, we use the 20th Century Reanalysis V2 (20CR), which spans the years 1871 to 2010, to statistically reconstruct daily maximum surge levels at a global scale. A multivariate linear regression model is fitted between daily mean ERA-interim sea level pressure fields and daily maximum surge levels from DAC. Following, the statistical model is used to reconstruct daily surges using mean sea level pressure fields from 20CR. The verification of the statistical model shows good agreements between DAC levels and the reconstructed surge levels from the 20CR. The validation of the reconstructed surge with tide gauges, distributed throughout the domain, shows good accuracy both in terms of high correlations and small errors. A time series comparison is also depicted at specific tide gauges for the beginning of the 20th century, showing a high concordance. Therefore, this work provides to the scientific community, a daily database of maximum surge levels; which correspond to an extension of the DAC database, from 1871 to 2010. This database can be used to improve the knowledge on historical storm surge conditions, allowing the study of their temporal and spatial variability.

Geology↗

PRECIOUS METALS IN SDSS QUASAR SPECTRA. I. TRACKING THE EVOLUTION OF STRONG, 1.5 < z < 4.5 C IV ABSORBERS WITH THOUSANDS OF SYSTEMS

We have vastly increased the C IV statistics at intermediate redshift by surveying the thousands of quasars in the Sloan Digital Sky Survey (SDSS) Data-Release 7. We visually verified over 16,000 C IV systems with 1.46 < z < 4.55-a sample size that renders Poisson error negligible. Detailed Monte Carlo simulations show that we are approximately 50% complete down to rest equivalent widths W {sub r} Almost-Equal-To 0.6 A. We analyzed the sample as a whole and in 10 small redshift bins with approximately 1500 doublets each. The equivalent width frequency distributions f(W {sub r}) were well modeled by an exponential, with little evolution in shape. In contrast with previous studies that modeled the frequency distribution as a single power law, the fitted exponential gives a finite mass density for the C IV ions. The comoving line density dN{sub CIV}/dX evolved smoothly with redshift, increasing by a factor of 2.37 {+-} 0.09 from z = 4.55-1.96, then plateauing at dN{sub CIV}/dX{approx}0.34 for z = 1.96-1.46. Comparing our SDSS sample with z < 1 (ultraviolet) and z > 5 (infrared) surveys, we see an approximately 10-fold increase in dN{sub CIV}/dX over z Almost-Equal-To 6 {yields} 0, for W {sub r} {>=} 0.6 A. This suggests a monotonic and significant increase in the enrichment of gas outside galaxies over the 12 Gyr lifetime of the universe.

79 ASTRONOMY AND ASTROPHYSICS↗

THE DEMOGRAPHICS OF BROAD-LINE QUASARS IN THE MASS-LUMINOSITY PLANE. II. BLACK HOLE MASS AND EDDINGTON RATIO FUNCTIONS

We employ a flexible Bayesian technique to estimate the black hole (BH) mass and Eddington ratio functions for Type 1 (i.e., broad line) quasars from a uniformly selected data set of {approx}58, 000 quasars from the Sloan Digital Sky Survey (SDSS) DR7. We find that the SDSS becomes significantly incomplete at M {sub BH} {approx}< 3 Multiplication-Sign 10{sup 8} M {sub Sun} or L/L {sub Edd} {approx}< 0.07, and that the number densities of Type 1 quasars continue to increase down to these limits. Both the mass and Eddington ratio functions show evidence of downsizing, with the most massive and highest Eddington ratio BHs experiencing Type 1 quasar phases first, although the Eddington ratio number densities are flat at z < 2. We estimate the maximum Eddington ratio of Type 1 quasars in the observable universe to be L/L {sub Edd} {approx} 3. Consistent with our results in Shen and Kelly, we do not find statistical evidence for a so-called sub-Eddington boundary in the mass-luminosity plane of broad-line quasars, and demonstrate that such an apparent boundary in the observed distribution can be caused by selection effect and errors in virial BH mass estimates. Based on the typical Eddington ratio in a given mass bin, we estimate growth times for the BHs in Type 1 quasars and find that they are comparable to or longer than the age of the universe, implying an earlier phase of accelerated (i.e., with higher Eddington ratios) and possibly obscured growth. The large masses probed by our sample imply that most of our BHs reside in what are locally early-type galaxies, and we interpret our results within the context of models of self-regulated BH growth.

79 ASTRONOMY AND ASTROPHYSICS↗

Deep Learning Experiments for Tropical Cyclone Intensity Forecasts

Reducing tropical cyclone (TC) intensity forecast errors is a challenging task that has interested the operational forecasting and research community for decades. To address this, we developed a deep learning (DL)-based multilayer perceptron (MLP) TC intensity prediction model. The model was trained using the global Statistical Hurricane Intensity Prediction Scheme (SHIPS) predictors to forecast the change in TC maximum wind speed for the Atlantic basin. In the first experiment, a 24-h forecast period was considered. To overcome sample size limitations, we adopted a leave one year out (LOYO) testing scheme, where a model is trained using data from all years except one and then evaluated on the year that is left out. When tested on 2010–18 operational data using the LOYO scheme, the MLP outperformed other statistical–dynamical models by 9%–20%. Additional independent tests in 2019 and 2020 were conducted to simulate real-time operational forecasts, where the MLP model again outperformed the statistical–dynamical models by 5%–22% and achieved comparable results as HWFI. The MLP model also correctly predicted more rapid intensification events than all the four operational TC intensity models compared. In the second experiment, we developed a lightweight MLP for 6-h intensity predictions. When coupled with a synthetic TC track model, the lightweight MLP generated realistic TC intensity distribution in the Atlantic basin. Therefore, the MLP-based approach has the potential to improve operational TC intensity forecasts, and will also be a viable option for generating synthetic TCs for climate studies.

58 GEOSCIENCES↗

Spectroscopic failures in photometric redshift calibration: cosmological biases and survey requirements

We use N-body-spectro-photometric simulations to investigate the impact of incompleteness and incorrect redshifts in spectroscopic surveys to photometric redshift training and calibration and the resulting effects on cosmological parameter estimation from weak lensing shear-shear correlations. The photometry of the simulations is modeled after the upcoming Dark Energy Survey and the spectroscopy is based on a low/intermediate resolution spectrograph with wavelength coverage of 5500{\AA} < {\lambda} < 9500{\AA}. The principal systematic errors that such a spectroscopic follow-up encounters are incompleteness (inability to obtain spectroscopic redshifts for certain galaxies) and wrong redshifts. Encouragingly, we find that a neural network-based approach can effectively describe the spectroscopic incompleteness in terms of the galaxies' colors, so that the spectroscopic selection can be applied to the photometric sample. Hence, we find that spectroscopic incompleteness yields no appreciable biases to cosmology, although the statistical constraints degrade somewhat because the photometric survey has to be culled to match the spectroscopic selection. Unfortunately, wrong redshifts have a more severe impact: the cosmological biases are intolerable if more than a percent of the spectroscopic redshifts are incorrect. Moreover, we find that incorrect redshifts can also substantially degrade the accuracy of training set based photo-z estimators. The main problem is the difficulty of obtaining redshifts, either spectroscopically or photometrically, for objects at z > 1.3. We discuss several approaches for reducing the cosmological biases, in particular finding that photo-z error estimators can reduce biases appreciably.

79 ASTRONOMY AND ASTROPHYSICS↗

Rates of adsorption and desorption: Entropic contributions and errors due to mean-field approximations

We have performed exact classical rate calculations to compute adsorption and desorption rate constants with a model representative of a real system. We compute the desorption rate using transition-state theory by taking the dividing-surface far from the surface of the solid. We find that using a mean-field assumption, i.e., applying potential of mean force to transition state theory, could lead to two orders-of-magnitude errors in the rate constant owing to large fluctuations in the desorption barrier. Furthermore, we compute the adsorption rate by including a dynamical factor which reflects the probability of sticking to the solid surface. We find that the sticking probability is highly sensitive to the coverage. Also, we find that the adsorption rate computed from the mean-field assumption is not very different from the exact adsorption rate. We also compute entropic contribution to desorption rates and compare it to that obtained from two limiting models of adsorption—2D ideal gas and 2D ideal lattice gas. We show that at high temperatures (700 K), the entropic contribution to desorption rates computed from the exact calculations is very close to that obtained from the 2D ideal gas model. However, for lower to intermediate temperatures from 200 K to 500 K, the entropic contributions cover a wide range which lies in between the two limiting models and could lead to over two-orders-of-magnitude errors in the rate coefficient.

Activation energies↗