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At least 757 records · Page 42

Simple hydrogenic estimates for the exchange and correlation energies of atoms and atomic ions, with implications for density functional theory

Exact density functionals for the exchange and correlation energies are approximated in practical calculations for the ground-state electronic structure of a many-electron system. An important exact constraint for the construction of approximations is to recover the correct non-relativistic large-Z expansions for the corresponding energies of neutral atoms with atomic number Z and electron number N = Z, which are correct to leading order (–0.221 Z 5/3 and –0.021 Z ln Z respectively) even in the lowest-rung or local density approximation. We find that hydrogenic densities lead to E x (N,Z) ≈ –0.354 N 2/3 Z (as known before only for Z >> N >> 1) and E c ≈ –0.02 N ln N . These asymptotic estimates are most correct for atomic ions with large N and Z >> N, but we find that they are qualitatively and semi- quantitatively correct even for small N and for N ≈ Z. The large-N asymptotic behavior of the energy is pre-figured in small-N atoms and atomic ions, supporting the argument that widely-predictive approximate density functionals should be designed to recover the correct asymptotics. Here, it is shown that the exact Kohn-Sham correlation energy, when calculated from the pure ground-state wavefunction, should have no contribution proportional to Z in the Z → ∞ limit for any fixed N.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Cathodic Protection Modeling for Hanford Underground Double-Shell Tank Farms

Hanford stores millions of gallons of radioactive and chemically hazardous waste from the production of weapon materials in tank farms consisting of underground carbon-steel storage tanks surrounded by reinforced concrete. Six of these Hanford tank farms use double-shell storage tanks (DSTs). The DST farms were constructed from 1968 to 1986 with a planned 40–50 year design life, so some are already operating beyond their initial life expectancy. Ultrasonic testing (UT) has indicated significant thinning on the bottom of the secondary (outer) liner of these tanks, believed to arise from groundwater intrusion driving concrete side corrosion. There is no direct access to the steel/concrete interface between the tank and the concrete pad, making it difficult to apply a chemical-based mitigation strategy or to conduct repairs, but cathodic protection (CP) is a possible method to inhibit further concrete-side corrosion. Hanford already uses CP to protect below grade steel piping within the tank farms and connected to the tanks, but this system was not designed to protect the tank bottoms. CP design must account for the structures surrounding the DSTs, including the steel reinforcing bars (rebar) within the concrete pad and vault, various process lines, and the existing CP system. In this study, finite element analysis (FEA) modeling was carried out to simulate CP protection of 1) a single tank and CP anode to develop options for modeling the rebar and to compare to a simpler circuit model and 2) the entire Hanford AN tank farm as a representative example consisting of seven tanks, associated piping, and both existing and new CP anodes. Both circuit and FEA models predict that significant protective current could be delivered to the bottoms of the tanks with the addition of tank-protection anodes below the depth of the tanks. Simulations with only the existing pipe-protection anodes active confirmed that only a very small current to the tank bottoms is predicted under present conditions. Multiple simplified representations of the dome and wall rebar were tested to reduce the computational complexity of the tank-farm simulations, resulting in modeling the rebar as edge elements with a prescribed effective circumference that matches the real rebar surface area. The geometry of the rebar is also simplified into horizontal hoops around the tank walls and radial rebar over the dome with increased effective circumference to retain the target surface area. This simplification was found to greatly reduce the complexity and solution time of the models without large changes in current distributions, especially to the tank bottom. A range of values were tested for model parameters such as soil and concrete resistivities and polarization resistance to investigate their impact on the current and electric potential distributions. Depending on the parameters used, FEA simulations predict some risk of overprotection, particularly on the piping system; since overprotection can also lead to surface damage associated with hydrogen gas generation at the interface (e.g. hydrogen embrittlement or damage to coatings), this needs to be considered when refining the design of the new CP system. Comparison between the FEA models and the circuit model representation demonstrated that the circuit model could not match the predicted FEA current distribution, even when using the exact same surface areas. This discrepancy appeared to be at least partly attributable to the impact of the relative positions of the tank components and anodes to each other and to the ground surface. The FEA model accounts for the relative positions since it solves the governing equations in three dimensions, but the circuit model cannot account for the positioning. In particular, the circuit model underpredicts the current to the tank bottom and overpredicts the current to the dome compared to FEA for the baseline geometry. The FEA models omitted the electrically isolated rebar in the bottom concrete slab. However, a circuit based stray current model estimated that only 2.1% of the total current through the slab would stray into the rebar, corresponding to ~0.21 A for a target current density of 2 mA/ft2 to the tank bottom. The estimated corrosion driven by this amount of stray current is predicted to yield a lifetime of >400 years for the minimum rebar diameter, assuming an acceptable cross-section area loss of 10%.

d'Entremont, Anna [Savannah River National Laborat↗

Wind power research at Oregon State University

There have been two primary thrusts of the research effort to date, along with several supplementary ones. One primary area has been an investigation of the wind fields along coastal areas of the Pacific Northwest, not only at the shoreline but also for a number of miles inland and offshore as well. Estimates have been made of the influence of the wind turbulence as measured at coastal sites in modifying the predicted dependence of power generated on the cube of the wind speed. Wind flow patterns in the Columbia River valley have also been studied. The second primary thrust has been to substantially modify and improve an existing wind tunnel to permit the build up of a boundary layer in which various model studies will be conducted. One of the secondary studies involved estimating the cost of building an aerogenerator.

Hewson, E. W.↗

Extinction Dynamics of the Foot-and-Mouth Disease Virus Carrier State Under Natural Conditions

Foot-and-mouth disease (FMD) is one of the most economically important livestock diseases worldwide. Following the clinical phase of FMD, a large proportion of ruminants remain persistently infected for extended periods. Although extinction of this carrier state occurs continuously at the animal and population levels, studies vary widely in their estimates of the duration of persistent infection. There is a need for robust statistical models to capture the dynamics of persistent infection for the sake of guiding FMD control and trade policies. The goal of the current study was to develop and assess statistical models to describe the extinction of FMD virus (FMDV) persistent infection using data from primary longitudinal studies of naturally infected cattle and Asian buffalo in Vietnam and India. Specifically, accelerated failure time (AFT) models and generalized linear mixed models (GLMM) were developed to predict the probability of persistent infection in seropositive animals and identified carriers at the individual animal level at sequential time points after outbreaks. The primary studies were analyzed by country and combined using an individual-participant data meta-analysis approach. The models estimated similar trends in the duration of persistent infection for the study/species groups included in the analyses, however the significance of the trends differed between the models. The overall probabilities of persistent infection were similar as predicted by the AFT and GLMM models: 6 months: 99% (AFT) /80% (GLMM), 12 months: 51% (AFT) /32% (GLMM), 18 months: 6% (AFT) /5% (GLMM), 24 months: 0.8% (AFT) /0.6% (GLMM). These models utilizing diverse and robust data sets predict higher probabilities of persistence than previously published, suggesting greater endurance of carriers subsequent to an outbreak. This study demonstrates the utility of statistical models to investigate the dynamics of persistent infection and the importance of large datasets, which can be achieved by combining data from several smaller studies in meta-analyses. Results of this study enhance current knowledge of the FMDV carrier state and may inform policy decisions regarding FMDV persistent infection.

59 BASIC BIOLOGICAL SCIENCES↗

Loss Factors for Small Distributed Wind Turbines Based on Field Data in the United States

While wind energy production loss due to unavailability, environmental impacts, curtailment, and other causes has been studied and characterized at the utility-scale wind farm level, observation-based characterization of project loss is lacking for distributed wind energy, particularly for projects involving small wind turbines. Contemporary tools and research that support pre-construction distributed wind energy characterization present a wide range of default loss factors to convert gross energy estimates to net: 7-18%. We hypothesize that we can use generation observations from operational distributed wind projects to develop more accurate representations of loss. Using a density-based filtering technique on distributed wind power generation timeseries, we determine periods of typical performance and use them with regression algorithms in a measure-correlate-predict fashion to simulate what the generation would have been during periods of atypical or unreported performance. From there, the actual versus predicted generation leads to the establishment of observation-informed loss factors (median = 17%) for small, single turbine installation distributed wind projects.

17 WIND ENERGY↗

A First–Principles–Based Sub–Lattice Formalism for Predicting Off–Stoichiometry in Materials for Solar Thermochemical Applications: The Example of Ceria

Theoretical models that reliably can predict off-stoichiometry in materials via accurate descriptions of underlying thermodynamics are crucial for energy applications. For example, transition-metal and rare-earth oxides that can tolerate a large number of oxygen vacancies, such as CeO 2 and doped CeO 2 , can split water and carbon dioxide via a two-step, oxide-based solar thermochemical (STC) cycle. The search for new STC materials with a performance superior to that of state-of-the-art CeO 2 can benefit from predictions accurately describing the thermodynamics of oxygen vacancies. The sub-lattice formalism, a common tool used to fit experimental data and build temperature-composition phase diagrams, can be useful in this context. Here, sub-lattice models are derived solely from zero-temperature quantum mechanics calculations to estimate fairly accurate temperature- and oxygen-partial-pressure-dependent off-stoichiometries in CeO 2 and Zr-doped CeO 2 . Physical motivations for deriving some of the “excess” sub-lattice model parameters directly from quantum mechanical calculations, instead of fitting to minimize deviations from experimental and/or theoretical data, are identified. As a result, important limitations and approximations of the approach used are specified and extensions to multi-cation oxides are also suggested to help identify novel candidates for water and carbon dioxide splitting and related applications.

08 HYDROGEN↗

Prospects for n -type doping of (Al x Ga 1– x ) 2 O 3 alloys

Here we systematically explore the properties of group-IV (C, Si, Ge, and Sn) and transition metal (Hf, Zr, and Ta) dopants substituting on the cation site in (Al x Ga 1– x ) 2 O 3 (AlGO) alloys using first-principles calculations with a hybrid functional. In Ga 2 O 3 , each of these dopants acts as a shallow donor. In Al 2 O 3 , they are deep defects characterized by the formation of either DX centers or positive- U (+/0) levels. Combining our calculations of dopant charge-state transition levels with information of the AlGO alloy band structure, we estimate the critical Al composition at which each dopant transitions from being a shallow to a deep donor. We identify Si to be the most efficient dopant to achieve n -type conductivity in high Al-content AlGO alloys, acting as a shallow donor over the entire predicted stability range for AlGO solid solution alloys.

36 MATERIALS SCIENCE↗

Quasi-two-dimensional Fermi surface of superconducting line-nodal metal CaSb 2

We report on the Fermi surfaces and superconducting parameters of CaSb 2 single crystals (superconducting below T c ~1.8K) grown by the self-flux method. The frequency of de Haas–van Alphen and Shubnikov–de Haas oscillations evidences a quasi-two-dimensional (quasi-2D) Fermi surface, consistent with one of the Fermi surfaces forming Dirac lines predicted by first-principles calculations. Measurements in the superconducting state reveal that CaSb 2 is close to a type-I superconductor with the Ginzburg-Landau parameter of around unity. The temperature dependence of the upper critical field H c2 is well described by a model considering two superconducting bands, and the enhancement of the effective mass estimated from H c2 (0K) is consistent with the quasi-2D band observed by the quantum oscillations. Our results indicate that a quasi-2D band forming Dirac lines contributes to the superconductivity in CaSb 2 .

36 MATERIALS SCIENCE↗

Response of U.S. West Coast Mountain Snowpack to Local Sea Surface Temperature Perturbations: Insights from Numerical Modeling and Machine Learning

Sea surface temperature (SST) significantly modulates the precipitation and temperature over land, with important consequences on land surface processes such as snowpack. Compared to the impact of remote SST, the effect of nearshore/local SST is less well understood. In this study, the impact of local SST on the mountain snowpack of the U.S. West Coast is investigated using two 6-km regional climate simulations driven by the same lateral boundary conditions but with time-varying versus time-invariant and warmer local SSTs during 2003–15. Results show that local SST warming leads to warmer winter with more precipitation over the mountains. Meanwhile, the removal of SST temporal variability results in reduced temperature variability but increased precipitation variability. As a result, winter snow accumulation decreases by ~200 mm per season in the Cascade Mountains in the north but increases by ~100 mm per season in the Sierra Nevada in the south. Such a dipole response results from the competing effects of precipitation and temperature change at different elevations and are amplified by the enhanced atmospheric river moisture transport. To further delineate the relative contributions of different meteorological factors to the snowpack response, two neural network models were developed to predict the snow behaviors at seasonal and monthly scales. These models reveal the dominant influence of the total amount and the average temperature of precipitation on the snowpack response. Furthermore, these findings highlight the sensitivity of mountain snowpack to local SST in the western United States and underscore the importance of local SST and atmospheric rives to accurate snowpack estimations for water management.

54 ENVIRONMENTAL SCIENCES↗

Hill-climbing controller for plants with any dynamics and rapid drifts.

Description of extremal control systems which utilize extrapolation procedures to optimize plant operations or processes involving any kind of dynamics before and after the static extremal characteristic. The optimization sequence starts with an 'action of drift detection' - i.e., a measurement of the drift rate of the output. Then a 'search action' is initiated which consists of stepped shifts of the input variable; the output response due to these changes in the input variable is evaluated in the light of the predicted shift and is used to provide information on the shape of the extremal characteristic at the actual operating point. The position of the extremum is estimated by a parabolic extrapolation of the shape of the characteristic from the operating point to the extremum. During the 'control action' the operating point is adjusted to the position corresponding to the predicted optimum of the process by first applying a forcing step to the input variable to obtain a quicker response at the beginning of the transient state, and then applying a definitive step to bring the input variable back to the position which corresponds to the predicted extremum. A 'rest time' may be introduced before starting the next optimization sequence.

Jacob, H. G.↗

Validation of the CQUAD4 element for vibration and shock analysis of thin laminated composite plate structure

The performance of the NASTRAN CQUAD4 membrane and plate element in the analysis of undamped natural vibration modes of thin fiber reinforced composite plates was evaluated. The element provides natural frequency estimates that are comparable in accuracy to alternative formulations, and, in most cases, deviate by less than 10 percent from experimentally measured frequencies. The predictions lie within roughly equal accuracy bounds for the two material types treated (GFRP and CFRP), and for the ply layups considered (unidirectional, cross-ply, and angle-ply). Effective elastic lamina moduli had to be adjusted for fiber volume fraction to attain this level of frequency. The lumped mass option provides more accurate frequencies than the consistent mass option. This evaluation concerned only plates with L/t ratios on the order of 100 to 150. Since the CQUAD4 utilizes first-order corrections for transverse laminate shear stiffness, the element should provide useful frequency estimates for plate-like structures with lower L/t. For plates with L/t below 20, consideration should be given to idealizing with 3-D solid elements. Based on the observation that natural frequencies and mode shapes are predicted with acceptable engineering accuracy, it is concluded that CQUAD4 should be a useful and accurate element for transient shock and steady state vibration analysis of naval ship

Lesar, Douglas E.↗

An Empirical Cumulus Parameterization Scheme for a Global Spectral Model

Realistic vertical heating and drying profiles in a cumulus scheme is important for obtaining accurate weather forecasts. A new empirical cumulus parameterization scheme based on a procedure to improve the vertical distribution of heating and moistening over the tropics is developed. The empirical cumulus parameterization scheme (ECPS) utilizes profiles of Tropical Rainfall Measuring Mission (TRMM) based heating and moistening derived from the European Centre for Medium- Range Weather Forecasts (ECMWF) analysis. A dimension reduction technique through rotated principal component analysis (RPCA) is performed on the vertical profiles of heating (Q1) and drying (Q2) over the convective regions of the tropics, to obtain the dominant modes of variability. Analysis suggests that most of the variance associated with the observed profiles can be explained by retaining the first three modes. The ECPS then applies a statistical approach in which Q1 and Q2 are expressed as a linear combination of the first three dominant principal components which distinctly explain variance in the troposphere as a function of the prevalent large-scale dynamics. The principal component (PC) score which quantifies the contribution of each PC to the corresponding loading profile is estimated through a multiple screening regression method which yields the PC score as a function of the large-scale variables. The profiles of Q1 and Q2 thus obtained are found to match well with the observed profiles. The impact of the ECPS is investigated in a series of short range (1-3 day) prediction experiments using the Florida State University global spectral model (FSUGSM, T126L14). Comparisons between short range ECPS forecasts and those with the modified Kuo scheme show a very marked improvement in the skill in ECPS forecasts. This improvement in the forecast skill with ECPS emphasizes the importance of incorporating realistic vertical distributions of heating and drying in the model cumulus scheme. This also suggests that in the absence of explicit models for convection, the proposed statistical scheme improves the modeling of the vertical distribution of heating and moistening in areas of deep convection.

Rajendran, K.↗

Deducing Land-Atmosphere Coupling Regimes from SMAP Soil Moisture

In recent years, there has been a growing recognition of the significance of Land-Atmosphere (L-A) interactions and feedback mechanisms in understanding and predicting Earth’s water and energy cycles. Soil moisture plays a critical role in mediating the strength of L-A interactions and is important for understanding the complex and governing processes across this interface. This study aims to identify the significance of soil moisture in identifying L-A coupling strength within the Convective Triggering Potential (CTP) and Humidity Index (HI) framework. To address this, a consistent and reliable dataset of atmospheric profiles is created by merging CTP and HI using Triple Collocation (TC) with three reanalysis datasets. The merged CTP and HI product demonstrates enhanced performance globally as compared to the individual datasets when validated with radiosonde and satellite observations. This merged product of CTP and HI is then used to compare the L-A coupling strength based on Soil Moisture Active Passive Level 3 (SMAPL3) and SMAP Level 4 (SMAPL4) over two decades (2003-2022) where L-A coupling strength is defined as the persistence probability within the dry and wet coupling regimes. Results indicate that the persistency-based coupling strength is related to the ability of soil moisture to predict future atmospheric humidity and dry vs. wet coupling state. The coupling strength in SMAPL4 is consistently stronger than in SMAPL3 and is likely due to its reliance on a land surface model and reduced susceptibility to random noise. The difference in coupling strength based on the same CTP-HI underscores the importance of soil moisture data in estimating coupling strength within the CTP-HI framework. These findings lay the groundwork for understanding the role of L-A interactions and drought evolution due to soil moisture variations, by providing insight into the quantification of coupling strength and its role in drought monitoring and forecast efforts.

Land-atmosphere coupling↗

Bridging the time scale in exascale computing of chemical systems (Final Technical Report)

This report summarizes the work carried out with support of the United States Department of Energy under Award DE-SC0019441. The theme of this project was to develop and apply methods that allowed for the acceleration of atomistic calculations, particularly in challenging areas such as multiphase systems, electrified interfaces, uncertainty estimation, and applications requiring chemical accuracy, which tend to be applications where simulation time is severely bottlenecked by the computational time requirements. Much of the focus was on the application of emerging machine-learning methodologies, although a wide range of methodologies were employed. This report has two major sections. The first focuses on the methodological advances themselves. Within this part, we report a number of major advances, a few examples of which are described here. We report the first machine-learning scheme for the acceleration of electronically grand-canonical calculations (that is, those applicable to electrochemistry). We report new methods of performing transfer learning, in which physics-based priors can be used to provide predictions, often with uncertainty estimates, of images well outside of training sets; we also offer ways to fine-tune these transfer-learning models. We provide a new systematic means to generate and apply minimal training data sets to very large (10,000’s of atoms) systems, with only small training sets appropriate for electronic structure. We developed new methodologies to integrate surface vibrations into surface adsorption calculations. We made advances to the applicability of diffusion Monte Carlo methods to allow (learned) force prediction, finite-size error correction, and force-free means of searching for transition states. We integrated machine-learned atomistic predictions into mechanism generation codes. Additionally, we released new software including AmpTorch, a modernized version of our original atomistic machine-learning code Amp. The second part of this report focuses on the scientific applications that accompanied, and were often enabled by, the methodological advances described earlier. A few examples follow, but full details are in the individual chapters of the report. For example, we developed a general theory of phonon-induced friction on molecular adsorbates. We showed fundamentally how solvent influences the adsorption and desorption process and how it differs from the processes typically involved at the solid–gas interface, making aqueous-phase and electrocatalysis different from traditional thermocatalysis. We examined how metal–insulator and magnetic transitions can be probed, and accelerated exciton dynamics via Frenkel Hamiltonian parameters. We showed that the nearsighted force-training approach, developed within this project, can predict both the stability and reactivity of large nanoparticles, and can also lead to insights on catalyst coverage on binding energies and entropies. These applied studies, which generally integrated with our method development, allowed us to push forward the theoretical understanding of several reaction classes.

08 HYDROGEN↗

JGI-Trichoderma v1.0

There is a series of Python and bash scripts to parse genomics datasets used to evaluate the coevolution of gene families and the feature importance of gene families using an SVM classifier. - Cover analysis: takes a list of single-copy genes in a set of genomes, aligns and builds the gene trees to determine if two gene families have a signature of covariation with one another. It parses the files to run phykit cover script described here: https://jlsteenwyk.com/PhyKIT/usage/index.html - SVM-classifier: This Python script is an SVM-based genomic classifier designed for biological data analysis. It combines machine learning with feature selection to identify important genomic markers and classify biological samples. Core Functionality: The script uses Support Vector Machines from scikit-learn to classify genomic data, incorporating SelectKBest for automated feature selection and leave-one-out cross-validation for performance assessment. It operates in multiple modes: feature ranking, optimal combination discovery, and sample prediction. Primary Applications: Genomic sample classification and biomarker discovery Feature importance analysis in high-dimensional biological datasets Prediction of sample categories based on genomic profiles Research applications requiring robust classification of biological data Key Advantages: High-dimensional handling: SVMs excel with genomic data's typical high feature-to-sample ratios Integrated feature selection: Reduces noise and computational overhead while identifying key markers Probability estimation: Provides confidence scores essential for biological interpretation Validation robustness: Leave-one-out cross-validation ensures reliable performance metrics Operational flexibility: Multiple analysis modes support different research phases from exploration to prediction

Stecca Steindorff, Andrei [Lawrence Berkeley Natio↗

Generalized Predictive Control for Active Stability Augmentation and Vibration Reduction on an Aeroelastic Tiltrotor Model

Tiltrotor aircraft are defining the state-of-the-art in vertical lift technology as they have the potential to greatly expand rotary-wing operational boundaries. However, they are often limited in forward flight speed due to complex coupled rotor and wing dynamic instabilities. The U.S. Army and NASA have been developing a new wind tunnel model, the TiltRotor Aeroelastic Stability Testbed(TRAST), to test proprotors in the NASA Langley Research Center Transonic Dynamics Tunnel (TDT) to investigate aeroelastic stability in cruise. The test is intended to provide high-quality research data for analytical tool development and validation. In addition, the TRAST model will support, develop, and mature new technologies for the design of advanced proprotor aircraft. Stability augmentation and vibration reduction during testing is planned with the use of an active control methodology known as Generalized Predictive Control(GPC). GPC is an autoregressive control law that experimentally acquires a system identification to derive the input-output relation of controls and corresponding sensors. This type of control law is especially useful for complex dynamic interactions that are difficult to explicitly model such as proprotor pylon instability, often referred to as whirl flutter. GPC has been successfully employed on other tiltrotor vehicles to suppress whirl flutter instabilities and vibrations. To aid in the characterization of the wind-tunnel model and in tool development, an analytical representation of the wind-tunnel model was developed using the rotorcraft comprehensive analysis system (RCAS) that simulates structural dynamics and aerodynamics. RCAS was used to derive state-space estimates of the physical plant at various flight conditions to test control law effectiveness. This paper will present an overview of the test article development, a description of RCAS, an explanation of the GPC methodology, and results of GPC being applied to state-space plant estimates of the TRAST model. In these simulations, GPC was effective at stabilizing the aircraft beyond the whirl-flutter boundary while simultaneously reducing vibrations across the flight regime. Additionally, a modern advancement to GPC, termed advanced GPC (AGPC), is introduced that enables a self-adapting system identification. Preliminary results show that AGPC is successful at self-correction as the plant changes from what was used for system identification.

tiltrotor↗

Pressure-dependent kinetics of cyclopentene consumption

Recent experiments have uncovered deficiencies in the ability of current kinetic models for cyclopentane combustion to predict species profiles as a function of O2 concentration. One likely source of these discrepancies flows from the limited availability of relevant kinetic data for key functionalized intermediates, requiring the use of distant analogies to estimate their rates. This work fills this gap for cyclopentene, the most prominent C5 intermediate in low-temperature cyclopentane combustion. Ab initio transition-state-theory based master equation methods are used to calculate pressure-dependent rate constants across four potential energy surfaces (C5H8 + OH, C5H8 + HO2, C5H7, and C5H7 + O2). Potential energy surfaces are characterized at the CCSD(T)-F12/cc-pVDZ-F12//revDSD-PBEP86-D3BJ/def2-TZVPP level of theory. Pressure-dependent rate constants and branching fractions are determined via 1D master equation calculations. The results are used to analyze the competition for radicals between cyclopentene and cyclopentane in the intermediate temperature region, and to identify the dominant pathways flowing from these initiation channels. On the OH initiation surface, we find good agreement with recently published experimental rate constants at high temperature, and we elucidate the complex temperature dependence below 800 K, where 𝜋𝜋 addition becomes prominent. On the HO2 initiation surface, we find an interesting alternative route to bicyclic ether formation via well-skipping over the HO2 adduct well. On the cyclopentenyl radical surface, the major product is cyclopentadiene plus H. On the cyclopentenyl + O2 surface, we find that resonance stabilization largely prevents the allylic radical from undergoing oxidation, whereas the alkylic radical has a somewhat elevated propensity for oxidation pathways relative to cyclopentyl.

ab initio calculations↗

Data-driven organic solubility prediction at the limit of aleatoric uncertainty

Abstract Small molecule solubility is a critically important property which affects the efficiency, environmental impact, and phase behavior of synthetic processes. Experimental determination of solubility is a time- and resource-intensive process and existing methods for in silico estimation of solubility are limited by their generality, speed, and accuracy. This work presents two models derived from the FASTPROP and CHEMPROP architectures and trained on BigSolDB which are capable of predicting solubility at arbitrary temperatures for a wide range of small molecules in organic solvent. Both extrapolate to unseen solutes 2–3 times more accurately than the current state-of-the-art model and we demonstrate that they are approaching the aleatoric limit (0.5–1$$\log S$$ log S ) of available test data, suggesting that further improvements in prediction accuracy require more accurate datasets. The FASTPROP-derived model (called FASTSOLV) and the CHEMPROP-based model are open source, freely accessible via a Python package and web interface, highly reproducible, and up to 2 orders of magnitude faster than current alternatives.

Science & Technology - Other Topics↗