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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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DOE OSTI2018

The Muon g-2 Experiment [Slides]

$a_{\mu} \equiv (g-2)/2$, most recently at Brookhaven National Lab (E821) in the early 2000s, differ from theoretical calculations by nearly 3.5\,$\sigma$. To address this discrepancy, the Muon $g-2$ Experiment at Fermilab (E989) has been designed to determine $a_{\mu}$ to a precision of 140 parts per billion, a four-fold improvement over the E821 measurement. This improved precision presents an excellent opportunity to uncover new physics beyond the standard model (BSM), and at minimum constrain BSM models. The E989 experiment is currently taking physics-quality data, to date having recorded nearly 60\% more statistics than was obtained at Brookhaven. An overview of the experimental technique will be discussed, along with an update of the run progress and selected hardware performance and analysis highlights.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2026

pop-cosmos : redshifts and physical properties of KiDS-1000 galaxies

ABSTRACT Principled Bayesian inference of galaxy properties has not previously been performed for wide-area weak-lensing surveys with millions of sources. We address this gap by applying the pop-cosmos generative model to perform spectral energy distribution (SED) fitting for 4 million KiDS (Kilo-Degree Survey)-1000 galaxies. Calibrated on deep COSMOS2020 photometric data, pop-cosmos specifies a physically motivated prior over the galaxy population up to $z \simeq 6$ in stellar population synthesis (SPS) parameter space. Using the Speculator SPS emulator with GPU (graphics processing unit)-accelerated Markov Chain Monte Carlo sampling, we perform full posterior inference at 8.2 GPU seconds per galaxy, obtaining joint constraints on galaxy redshifts and physical properties. We validate photometric redshifts against $\sim \!185\,\!000$ KiDS galaxies cross-matched to Dark Energy Spectroscopic Instrument Data Release 1 spectroscopic samples, achieving low bias ($2\times 10^{-3}$), scatter ($\sigma _{\mathrm{MAD}}=0.03$), and outlier fraction (3.2 per cent) for the Bright Galaxy Survey, with comparable performance (bias $3\times 10^{-2}$, $\sigma _{\mathrm{MAD}}=0.05$, 1.0 per cent outliers) for luminous red galaxies (LRGs). Within the LRG sample, we identify massive, dusty, star-forming contaminants at $z \simeq 0.4$ satisfying standard colour selections for quenched populations. We infer trends in stellar mass, star formation, metallicity, and dust across five tomographic redshift bins consistent with established scaling relations. Using specific star formation rate constraints, we identify $\sim$7 per cent of KiDS-1000 galaxies as quenched, versus 37 per cent implied by conservative colour cuts. This enables the construction of weak-lensing samples defined by physical properties while mitigating intrinsic alignment systematics and preserving statistical power. Our analysis validates pop-cosmos out of sample, establishing it as a scalable approach for galaxy evolution and cosmological analyses with photometric surveys.

Halder, Anik [Institute of Astronomy and Kavli Ins↗
DOE OSTI2014

Relative brightness of the O{sup +}({sup 2} D-{sup 2} P) doublets in low-energy aurorae

The ratio of the emission line doublets from O{sup +} at 732.0 nm (I {sub 732}) and 733.0 nm (I {sub 733}) has been measured in auroral conditions of low-energy electron precipitation from Svalbard (78.°20 north, 15.°83 east). Accurate determination of R = I {sub 732}/I {sub 733} provides a powerful method for separating the density of the O{sup +} {sup 2} P{sub 1} {sub /2,3} {sub /2}{sup o} levels in modeling of the emissions from the doublets. A total of 383 spectra were included from the winter of 2003-2004. The value obtained is R = I {sub 732}/I {sub 733} = 1.38 ± 0.02, which is higher than theoretical values for thermal equilibrium in fully ionized plasma, but is lower than reported measurements by other authors in similar auroral conditions. The continuity equations for the densities of the two levels are solved for different conditions, in order to estimate the possible variations of R. The results suggest that the production of ions in the two levels from O ({sup 3} P {sub 1}) and O ({sup 3} P {sub 2}) does not follow the statistical weights, unlike astrophysical calculations for plasmas in nebulae. The physics of auroral impact ionization may account for this difference, and therefore for the raised value of R. In addition, the auroral solution of the densities of the ions, and thus of the value of R, is sensitive to the temperature of the neutral atmosphere. Although the present work is a statistical study, it shows that it is necessary to determine whether there are significant variations in the ratio resulting from non-equilibrium conditions, from auroral energy deposition, large electric fields, and changes in temperature and composition.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2013

Reply to Comment by S. E. Yuter et al. on 'Why do Tornados and Hailstorms Rest on Weekends?'

We show here that none of the concerns of Yuter et al. [2013, hereinafter Y2013] have any validity. We use this opportunity to clarify issues that may have been misunderstood by some readers (Y2013 among them) of Rosenfeld and Bell [2011, hereinafter RB2011], elaborate on our explanations there and further substantiate the evidence showing the impacts of aerosols on severe convective storms and the ways by which they are manifested in the weekly cycle. [2] Y2013 raise two general questions concerning the evidence for a weekly cycle of tornadoes given by RB2011: (1) whether the statistical analysis is valid, and (2) whether the discussion of physical mechanisms that explain the weekly cycle is correct. [3] In section 2, we show that there is no basis for the criticisms of Y2013 concerning the physical mechanisms proposed in RB2011 behind the observed changes in tornado activity and show further the mechanism by which aerosols can modulate tornadoes. Most of the comments by Y2013 appear to result from a misunderstanding and misinterpretation of RB2011. In section 3, we show that the comments by Y2013 concerning the statistical analysis are either incorrect or irrelevant. Some of the questions they raised were already answered previously by RB2011, and references therein. We also show that the complaint of Y2013, that the spatial averaging used in RB2011 inappropriately blends tornado behavior of different kinds in different regions, is unfounded.

severe storms↗
DOE OSTI2015

Enhancing the interaction between nuclear experiment and theory through information and statistics

This Focus Issue draws from a range of topics within nuclear physics, from studies of individual nucleons to the heaviest of nuclei. The unifying theme, however, is to illustrate the extent to which uncertainty is a key quantity, and to showcase applications of the latest computational methodologies. It is our assertion that a paradigm shift is needed in nuclear physics to enhance the coupling between theory and experiment, and we hope that this collection of articles is a good start.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2010

Exploring a Physically Based Tool for Lightning Cessation: A Preliminary Study

The University of Alabama in Huntsville (UA Huntsville) and NASA's Marshall Space Flight Center are collaborating with the 45th Weather Squadron (45WS) at Cape Canaveral Air Force Station (CCAFS) to enable improved nowcasting of lightning cessation. The project centers on use of dual-polarimetric radar capabilities, and in particular, the new C-band dual-polarimetric weather radar acquired by the 45WS. Special emphasis is placed on the development of a physically based operational algorithm to predict lightning cessation. While previous studies have developed statistically based lightning cessation algorithms, we believe that dual-polarimetric radar variables offer the possibility to improve existing algorithms through the inclusion of physically meaningful trends reflecting interactions between in-cloud electric fields and microphysics. Specifically, decades of polarimetric radar research using propagation differential phase has demonstrated the presence of distinct phase and ice crystal alignment signatures in the presence of strong electric fields associated with lightning. One question yet to be addressed is: To what extent can these ice-crystal alignment signatures be used to nowcast the cessation of lightning activity in a given storm? Accordingly, data from the UA Huntsville Advanced Radar for Meteorological and Operational Research (ARMOR) along with the North Alabama Lightning Mapping Array are used in this study to investigate the radar signatures present before and after lightning cessation. A summary of preliminary results will be presented.

Schultz, Elise V.↗
NASA NTRS2010

Exploring a Physically Based Tool for Lightning Cessation: Preliminary Results

The University of Alabama in Huntsville (UAHuntsville) and NASA s Marshall Space Flight Center are collaborating with the 45th Weather Squadron (45WS) at Cape Canaveral Air Force Station (CCAFS) to enable improved nowcasting of lightning cessation. The project centers on use of dual-polarimetric radar capabilities, and in particular, the new C-band dual-polarimetric weather radar acquired by the 45WS. Special emphasis is placed on the development of a physically based operational algorithm to predict lightning cessation. While previous studies have developed statistically based lightning cessation algorithms, we believe that dual-polarimetric radar variables offer the possibility to improve existing algorithms through the inclusion of physically meaningful trends reflecting interactions between in-cloud electric fields and microphysics. Specifically, decades of polarimetric radar research using propagation differential phase has demonstrated the presence of distinct phase and ice crystal alignment signatures in the presence of strong electric fields associated with lightning. One question yet to be addressed is: To what extent can these ice-crystal alignment signatures be used to nowcast the cessation of lightning activity in a given storm? Accordingly, data from the UAHuntsville Advanced Radar for Meteorological and Operational Research (ARMOR) along with the North Alabama Lightning Mapping Array are used in this study to investigate the radar signatures present before and after lightning cessation. A summary of preliminary results will be presented.

Schultz, Elsie V.↗
NASA NTRS2011

Exploring the Use of Radar for a Physically Based Lightning Cessation Nowcasting Tool

NASA s Marshall Space Flight Center (MSFC) and the University of Alabama in Huntsville (UAHuntsville) are collaborating with the 45th Weather Squadron (45WS) at Cape Canaveral Air Force Station (CCAFS) to enable improved nowcasting of lightning cessation. This project centers on use of dual-polarimetric radar capabilities, and in particular, the new C-band dual-polarimetric weather radar acquired by the 45WS. Special emphasis is placed on the development of a physically based operational algorithm to predict lightning cessation. While previous studies have developed statistically based lightning cessation algorithms, we believe that dual-polarimetric radar variables offer the possibility to improve existing algorithms through the inclusion of physically meaningful trends reflecting interactions between in-cloud electric fields and hydrometeors. Specifically, decades of polarimetric radar research using propagation differential phase has demonstrated the presence of distinct phase and ice crystal alignment signatures in the presence of strong electric fields associated with lightning. One question yet to be addressed is: To what extent can these ice-crystal alignment signatures be used to nowcast the cessation of lightning activity in a given storm? Accordingly, data from the UAHuntsville Advanced Radar for Meteorological and Operational Research (ARMOR) along with the NASA-MSFC North Alabama Lightning Mapping Array are used in this study to investigate the radar signatures present before and after lightning cessation. Thus far, our case study results suggest that the negative differential phase shift signature weakens and disappears after the analyzed storms ceased lightning production (i.e., after the last lightning flash occurred). This is a key observation because it suggests that while strong electric fields may still have been present, the lightning cessation signature encompassed the period of the polarimetric negative phase shift signature. To the extent this behavior is repeatable in other cases, even if only in a substantial fraction of those cases, the case analyses suggests that differential propagation phase may prove to be a useful parameter for future lightning cessation algorithms. Indeed, analysis of 15+ cases has shown additional indications of the weakening and disappearance of this ice alignment signature with lightning cessation. A summary of results will be presented.

Schultz, Elise V.↗
DOE OSTI2016

Characterization of 3D Cirrus Cloud and Radiation Fields Using ARS/AIRS/MODIS data and its Application to Climate Model

During the report period, we have made the following research accomplishments. First, we performed analysis for a number of MODIS scenes comprising of heavy dust events and ice clouds, covering regions of frequent dust outbreaks in East Asia, Middle East, and West Africa, as well as areas associated with long-range dust transports over the Equatorial Tropical Atlantic Ocean. These scenes contain both dust/aerosols and clouds. We collected suitable aerosol/ice-cloud data, correlated ice cloud and aerosol parameters by means of statistical analysis, and interpreted resulting correlation trends based on the physical principles governing cloud microphysics. Aerosol and cloud optical depths and cloud effective particle size inferred from MODIS for selected domains were analyzed from which the parameters including dust aerosol number concentration, ice cloud water path, and ice particle number concentration were subsequently derived. We illustrated that the Twomey (solar albedo) effect can be statistically quantified based on the slope of best-fit straight lines in the correlation study. Analysis of aerosol and cloud retrieval products revealed that for all cases, the region with a larger dust aerosol optical depth is always characterized by a smaller cloud particle size, consistent with the Twomey hypothesis for aerosol-cloud interactions. Second, we developed mean correlation curves with uncertainties associated with small ice-crystal concentration observations for the mean effective ice crystal size (De) and ice water content (IWC) by dividing the atmosphere into three characteristic regions: Tropics cirrus, Midlatitude cirrus, including a temperature classification to improve correlation, and Arctic ice clouds. We illustrated that De has a high correlation with IWC based on theoretical consideration and analysis of thousands of observed ice crystal data obtained from a number of ARM-DOE field campaigns and other experiments. The correlation has the form: ln(De) = a + b ln(IWC) + c ((ln(IWC))2, where a, b, and c are fitting coefficients and are functions of three regions. We demonstrated that this correlation can be effectively incorporated in GCMs and climate models that predict IWC - a significant advance in ice microphysics parameterization for interactive cloud-radiation analysis and feedback. Substantial July mean differences are shown in the OLR (W/m2) and precipitation (mm/day) patterns between UCLA GCM simulations based on Des determined from the De-IWC correlations and the control run using a fixed ice crystal size. Third, in order to improve the computation of spectral radiative transfer processes in the WRF model, we developed a consistent and efficient radiation scheme that can better resolve the spectral bands, determine the cloud optical properties, and provide more reliable and accurate radiative heating fields. In the newly developed radiation module, we have implemented in WRF a modified and improved version referred to as the Fu-Liou-Gu scheme, which includes a combination of delta-four-stream and delta-two-stream approximations for solar and IR flux calculations, respectively. This combination has been proven to be computationally efficient and at the same time to produce a high degree of accuracy. The incorporation of nongray gaseous absorption in multiple scattering atmospheres was based on the correlated k-distribution method. The solar and IR spectra are divided into 6 and 12 bands, respectively, according to the location of absorption bands of H2O, CO2, O3, CH4, N2O, and CFCs. We further included absorption by the water vapor continuum and a number of minor absorbers in the solar spectrum leading to an additional absorption of solar flux in a clear atmosphere on the order of 1-3 W/m2. Additionally, we incorporated the ice microphysics parameterization that includes an interactive mean effective ice crystal size in association with radiation parameterizations. The Fu-Liou-Gu scheme is an ideal tool for the simulation of radiative transfer and ice microphysics within the domain of WRF. It is particularly useful for studying direct and indirect aerosol radiative effects associated with ice cloud formation. The newly implemented radiation module has been demonstrated to work well in WRF and can be effectively used for studies related to cirrus cloud formation and evolution as well as aerosol-cloud-radiation interactions. With the newly implemented radiation scheme, the simulations of cloud cover and ice water path have been improved for cirrus clouds, with a more consistent comparison with the corresponding MODIS observations, especially for optically thin cirrus with an improvement of about 20% in the simulated mean ice water path.

97 MATHEMATICS AND COMPUTING↗
NASA NTRS1993

Coherent Doppler lidar signal covariance including wind shear and wind turbulence

The performance of coherent Doppler lidar is determined by the statistics of the coherent Doppler signal. The derivation and calculation of the covariance of the Doppler lidar signal is presented for random atmospheric wind fields with wind shear. The random component is described by a Kolmogorov turbulence spectrum. The signal parameters are clarified for a general coherent Doppler lidar system. There are two distinct physical regimes: one where the transmitted pulse determines the signal statistics and the other where the wind field dominates the signal statistics. The Doppler shift of the signal is identified in terms of the wind field and system parameters.

Frehlich, R. G.↗
DOE OSTI2019

Collaborative Research: Experimental and Theoretical Study of the Plasma Physics of Antihydrogen Generation and Trapping (Final Technical Report)

The charge-parity-time (CPT) invariance principle and the weak equivalence principle (WEP) undergird our current understanding of Nature. CPT, which is based on only Lorentz invariance, locality, and spin-statistics, is basic to local relativistic quantum field theory (QFT) models of physical laws. Testing established principles like these is a long-standing and honorable tradition in physics. Beginning with Newton’s Laws, many firmly established laws have been superseded, often to the great surprise of contemporaneous physicists. Certainly, CPT rests on firmer grounds than the earlier widely believed, but erroneous principles, of parity (P) and charge-parity (CP) invariance, but this does not necessarily make CPT inviolable. Tests of CPT confront the entire framework of QFT, and are quite distinct from most other “beyond the Standard Model” searches, which look for new physics within the QFT framework. With the failure, so far, to find new physics at the LHC or in dark matter searches, the motivation to test QFT itself is urgent. The revolutionary consequences of CPT and WEP violation would be so great that these principles are under intense scrutiny in many different systems. Here we focus on tests of CPT and WEP that employ antimatter, specifically antihydrogen. Such tests are difficult to realize experimentally, but constitute some of the simplest and most profound matter-antimatter comparisons that can be performed. Antimatter particles have been investigated since the prediction and subsequent discovery of the positron in the 1930s. That early discovery motivated the search for the antiproton, culminating in its creation and detection in Berkeley two decades later. As far as we know today, particles and their antiparticles share identical properties except for the sign of their charge. Antihydrogen is the simplest antimatter system—it is the antiparticle of the simplest atom, hydrogen. Differences between the spectra of the two are forbidden by CPT. The weak equivalence principle (WEP), demands that matter and antimatter accelerate identically in a gravitational field. WEP has never been subjected to a direct, free fall test using antimatter. Because of the weakness of the gravita tional force, direct antimatter WEP tests must employ a neutral particle, of which antihydrogen is the simplest to obtain. There are reasons to suspect that something is amiss with our understanding of antimatter. All generally accepted theories of the Big Bang predict that roughly equal amounts of matter and antimatter should have been created. Instead, very little antimatter has been observed in the Universe. This baryogenesis problem is arguably the most fundamental issue with the theory of the Big Bang. Its resolution may come from the discovery of enhanced CP violation, but could also come from CPT or WEP violation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Uncertainty quantification of effective nuclear interactions

We give a brief review on the development of phenomenological NN interactions and the corresponding quanti cation of statistical uncertainties. We look into the uncertainty of effective interactions broadly used in mean eld calculations through the Skyrme parameters and effective eld theory counter-terms by estimating both statistical and systematic uncertainties stemming from the NN interaction. We also comment on the role played by different tting strategies on the light of recent developments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2024

A Physics-Based Antarctic Melt Detection Technique: Combining Advanced Microwave Scanning Radiometer 2, Radiative-Transfer Modeling, and Firn Modeling

Surface melt on ice shelves has been linked to hydrofracture and subsequent ice shelf breakup. Since the 1990s, scientists have been using microwave radiometers to detect melt on ice shelves and ice sheets by applying various statistical thresholding techniques to identify significant increases in brightness temperature that are associated with melt. In this study, instead of using a fixed threshold, we force the Snow Radiative Transfer model (SMRT) with outputs from the Community Firn Model (CFM) to create a dynamic, physics-based threshold for melt. In the process, we also combine our method with statistical thresholding techniques and produce microwave grain size information in the process. We run this “Hybrid Method” across the Larsen C ice shelf as well as thirteen sites on the Antarctic Ice Sheet. Melt and non-melt days from the Hybrid Method and three statistical thresholding techniques match with surface energy balance within 94±1%; the effect of melt on the passive microwave is mostly binary and thus largely detectable by statistical thresholding techniques as well as physics-based techniques. Rather than always replacing statistical thresholding techniques with the Hybrid Method, we recommend using the Hybrid Method in studies where melt volume or grain size is of interest. In this study, we show that the Hybrid Method can be used to (a) model dry snow brightness temperatures of Antarctic snow and (b) derive a measure of grain size; therefore, it is an important step forwards towards using firn and radiative transfer modeling to quantify melt rather than to simply detect melt days.

Marissa E Dattler↗
DOE OSTI2024

Probabilistic neural networks for improved analyses with phenomenological R -matrix

Here we present a method for measurement analyses based on probabilistic deep neural networks that provide several advantages over conventional analyses with phenomenological models. These include predicting physical quantities directly from data, the rapid generation of statistically robust uncertainties, and the ability to bypass some parameters that may induce ambiguities and complications in data analysis. As deep learning methods make predictions through “black boxes,” the uncertainty quantification is typically challenging. We use a probabilistic framework that provides thorough uncertainty quantification and is straightforward to follow in practice. With the network architecture based on the Transformer, we demonstrate the current method for predicting nuclear resonance parameters from scattering data using the phenomenological R-matrix model.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Quantitative metrics for evaluating thermonuclear design codes and physics models applied to the National Ignition Campaign

In this study, physics models and design codes for hot dense plasmas undergoing thermonuclear burn are evaluated objectively using statistical metrics that compare the difference between calculations and data relative to the experimental uncertainties. The analysis is applied to the National Ignition Campaign (NIC) because it is relevant, comprehensive, and well documented. The statistics confirm that a key process afflicting NIC performance is mix driven by hydrodynamic instabilities as approximated here using the KL model [G. Dimonte and R. Tipton, Phys. Fluids 18, 085101 (2006)]. New physics models are also presented for instability-driven magnetic fields [B. Srinivasan et al., Phys. Rev. Lett. 108, 165002 (2012)] and the Coulomb logarithm for electron–ion thermal relaxation [G. Dimonte and J. Daligault, Phys. Rev. Lett. 101, 135001 (2008)]. The plasma-generated magnetic fields improve the agreement between code and data in a statistically significant manner by reducing the electron thermal conduction in the hot-spot via the Hall term. The Coulomb logarithm is presented in a numerically practical form that incorporates recent theoretical advances. However, it does not improve the agreement between the code and data because the thermal relaxation is so fast in non-ignited NIC plasmas that the typical 20% error does not change the tight coupling between electrons and ions. Even with these improved physics models, the one-dimensional simulations presented here are not able to describe the high-convergence NIC implosions in a statistically acceptable manner. Of the heroic multi-dimensional simulations of Clark et al. [Phys. Plasmas 23, 056302 (2016)], only those in three-dimensions satisfy the statistical acceptance criterion.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Python GST Implementation (PyGSTi) v. 0.9

PyGSTi is a Python package for modeling and characterizing noise (errors) in small quantum information processors. In addition to being a basic framework for describing quantum circuits and noise models, it implements mainstream quantum characterization, verification, and validation (QCVV) protocols such as Gate Set Tomography (GST), Randomized Benchmarking (RB), Robust Phase Estimation, and Idle Tomography. It also implements prototype protocols used for timeseries analysis and crosstalk detection, all of which have the goal of better understanding the noise found in existing as-built experimental devices. The central protocol of pyGSTi (from where it derives its name) is Gate Set Tomography. GST is a theory and protocol for simultaneously estimating the state preparation, gate operations, and measurement effects of a physical system of one or many quantum bits (qubits). These estimates are based entirely on the statistics of experimental measurements, and their interpretation and analysis can provide a detailed understanding of the types of errors/imperfections in the physical system. In this way, GST provides not only a means of certifying the “goodness” of qubits but also a means of debugging (i.e. improving) them. The other protocols follow this similar pattern in that they use statistical inference and analysis of experimental data to estimate one or more properties of the noise in a device.

Nielsen, Erik↗
DOE OSTI2021

Data Science Meets Physical Organic Chemistry

At the heart of synthetic chemistry is the holy grail of predictable catalyst design. In particular, researchers involved in reaction development in asymmetric catalysis have pursued a variety of strategies toward this goal. This is driven by both the pragmatic need to achieve high selectivities and the inability to readily identify why a certain catalyst is effective for a given reaction. While empiricism and intuition have dominated the field of asymmetric catalysis since its inception, enantioselectivity offers a mechanistically rich platform to interrogate catalyst-structure response patterns that explain the performance of a particular catalyst or substrate. In the early stages of an asymmetric reaction development campaign, the overarching mechanism of the reaction, catalyst speciation, the turnover limiting step, and many other details are unknown or posited based on related reactions. Considering the unclear details leading to a successful reaction, initial enantioselectivity data are often used to intuitively guide the ultimate direction of optimization. However, if the conditions of the Curtin-Hammett principle are satisfied, then measured enantioselectivity can be directly connected to the ensemble of diastereomeric transition states (TSs) that lead to the enantiomeric products, and the associated free energy difference between competing TSs (ΔΔ G ‡ = - RT ln[( S )/( R )], where ( S ) and ( R ) represent the concentrations of the enantiomeric products). We, and others, speculated that this important piece of information can be leveraged to guide reaction optimization in a quantitative way. Although traditional linear free energy relationships (LFERs), such as Hammett plots, have been used to illuminate important mechanistic features, we sought to develop data science derived tools to expand the power of LFERs in order to describe complex reactions frequently encountered in modern asymmetric catalysis. Specifically, we investigated whether enantioselectivity data from a reaction can be quantitatively connected to the attributes of reaction components, such as catalyst and substrate structural features, to harness data for asymmetric catalyst design. In this context, we developed a workflow to relate computationally derived features of reaction components to enantioselectivity using data science tools. The mathematical representation of molecules can incorporate many aspects of a transformation, such as molecular features from substrate, product, catalyst, and proposed transition states. Statistical models relating these features to reaction outputs can be used for various tasks, such as performance prediction of untested molecules. Perhaps most importantly, statistical models can guide the generation of mechanistic hypotheses that are embedded within complex patterns of reaction responses. Overall, merging traditional physical organic experiments with statistical modeling techniques creates a feedback loop that enables both evaluation of multiple mechanistic hypotheses and future catalyst design. In this Account, we highlight the evolution and application of this approach in the context of a collaborative program based on chiral phosphoric acid catalysts (CPAs) in asymmetric catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Enskog Equation for Confined Elastic Hard Spheres

A kinetic equation for a system of elastic hard spheres or disks confined by a hard wall of arbitrary shape is derived. It is a generalization of the modified Enskog equation in which the effects of the confinement are taken into account and it is supposed to be valid up to moderate densities. From the equation, balance equations for the hydrodynamic fields are derived, identifying the collisional transfer contributions to the pressure tensor and heat flux. A Lyapunov functional, H[f], is identified. For any solution of the kinetic equation, H decays monotonically in time until the system reaches the inhomogeneous equilibrium distribution, that is a Maxwellian distribution with a density field consistent with equilibrium statistical mechanics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗