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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Multi-modal Energy-optimal Trip Scheduling in Real-time (METS-R) for Transportation Hubs (Final Report)

This report summarizes the work performed under the award number EE0008524. The project develops the Multi-modal Energy-optimal Trip Scheduling in Real-time (METS-R) platform as the next-generation transportation solution based on autonomous electric vehicles (AEV) serving passenger trips from and to urban transportation hubs, to substantially reduce transportation energy consumption. Extensive data collection and analyses were first conducted to understand the demand patterns and energy consumption of hub-based on-road trips. Then, a data-driven framework that consists of an analytical module and a simulation module was proposed. For the analytical module, five planning + operation tools were developed to support the planning and energy-efficient operations of urban AEV services: the charging station planning that robotically allocates charging supplies based on the stationary charging demand distribution; the transit planning and demand adaptive scheduling model that efficiently generates\ candidate transit routes from hubs to other places and dynamically adjusts the transit time table to fit the current demand; the online energy-efficient routing that learns the energy-optimal paths from observations of link-level energy consumption in real-time; the hub-based ridesharing that matches trip requests together with account for the uncertainty of future trip demand and vehicle supply; and finally, the integrated demand prediction and anomaly detection pipeline that leverages the flight/train time table and support other planning/operation tools. To demonstrate the performance of these tools, a scalable high-performance agent-based simulator was built. We divided the urban space into multiple service zones where each zone was considered as an agent for passenger generation and vehicle charging. Two types of AEV agents were coded to model two types of mobility services: AEV taxi and AEV transit. For the AEV taxi, the team implemented the functions of pickup/drop-off passengers, energy-efficient routing, ridesharing, fleet rebalancing, and recharging. For the AEV bus, the team implemented the functions of demand-adaptive route scheduling, passenger boarding, and recharging. A high-performance computing framework was introduced to receive various profiling information (such as link energy updates, vehicle speed) from the simulator instances and communicate the operational commands back to the instances. The numerical experiments show that each of the proposed operational algorithms can reduce energy consumption and improve system efficiency. Furthermore, there exists the need to collectively consider multiple planning + operational strategies as multiple strategies can influence each other in terms of performance impacts. Recommendations for future work related to AEV planning and simulation are discussed.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2019

Clean and Convenient Tessellations for Number Counting Jastrow Factors

We introduce a basis of counting functions that, by cleanly tessellating three-dimensional space, allows real space number counting Jastrow factors to be straightforwardly applied to general molecular situations. Here, by exerting direct control over electron populations in local regions of space and encoding pairwise correlations between these populations, these Jastrow factors allow even very simple reference wave functions to adopt nodal surfaces well suited to many strongly correlated settings. Being trivially compatible with traditional Jastrow factors and diffusion Monte Carlo and having the same cubic per-sample cost scaling as a single determinant trial function, these Jastrow factors thus offer a powerful new route to the simultaneous capture of weak and strong electron correlation effects in a wide variety of molecular and materials settings. In multiple strongly correlated molecular examples, we show that even when paired with the simplest possible single determinant reference, these Jastrow factors allow quantum Monte Carlo to out-perform coupled cluster theory and approach the accuracy of traditional multireference methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations

The quasiclassical trajectory (QCT) method is an efficient and important tool for studying the dynamics of bimolecular reactions. In this method, the motion of the atoms is simulated classically, and the only quantum effect considered is that the initial vibrational states of reactant molecules are semiclassically quantized. A sensible expectation is that the initial ensemble of classical molecular states generated this way should be stationary, similarly to the quantum state it is supposed to represent. The most widely used method for sampling the vibrational phase space of polyatomic molecules is based on the normal mode approximation. In the present work, it is demonstrated that normal mode sampling provides a nonstationary ensemble even for a simple molecule like methane, because real potential energy surfaces are anharmonic in the reactant domain. The consequences were investigated for reaction CH{sub 4} + H → CH{sub 3} + H{sub 2} and its various isotopologs and were found to be dramatic. Reaction probabilities and cross sections obtained from QCT calculations oscillate periodically as a function of the initial distance of the colliding partners and the excitation functions are erratic. The reason is that in the nonstationary ensemble of initial states, the mean bond length of the breaking C–H bond oscillates in time with the frequency of the symmetric stretch mode. We propose a simple method, one-period averaging, in which reactivity parameters are calculated by averaging over an entire period of the mean C–H bond length oscillation, which removes the observed artifacts and provides the physically most reasonable reaction probabilities and cross sections when the initial conditions for QCT calculations are generated by normal mode sampling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Molecular Engineering of Hydroxide Conducting Polymers for Anion Exchange Membranes in Electrochemical Energy Conversion Technology

Anion exchange membranes (AEMs) based on hydroxide-conducting polymers (HCPs) are a key component for anion-based electrochemical energy technology such as fuel cells, electrolyzers, and advanced batteries. Although these alkaline electrochemical applications offer a promising alternative to acidic proton exchange membrane electrochemical devices, access to alkaline-stable and high-performing polymer electrolyte materials has remained elusive until now. Despite vigorous research of AEM polymer design, literature examples of high-performance polymers with good alkaline stability at an elevated temperature are uncommon. Traditional aromatic polymers used in AEM applications contain a heteroatomic backbone linkage, such as an aryl ether bond, which is prone to degradation via nucleophilic attack by hydroxide ion. In this Account, we highlight some of the progress our group has made in the development of advanced HCPs for applications in AEMs and electrode ionomers. Here, we propose that a synthetic polymer design with an all C−C bond backbone and a flexible chain-tethered quaternary ammonium group provides an effective solution to the problem of alkaline stability. Because of the critical demand for such a polymer system, we have established new synthetic strategies for polymer functionalization and polycondensation using an acid catalyst. The first approach is to graft a cationic tethered alkyl group to pre-existing, commercially available styrene-based block copolymers. The second approach is to synthesize high-molecular-weight aromatic backbone polymers using acid-catalyzed polycondensation of arene monomers and a functionalized trifluoromethyl ketone substrate. Both strategies involve a simple two-step reaction process and avoid the use of expensive metal-based catalysts and toxic chemicals, thereby making the synthetic processes easily scalable to large industrial quantities. Both polymer systems were found to have excellent alkaline stability, confirmed by the preservation of ion exchange capacity and ion conductivity of the membrane after an alkaline test under conditions of 1 M NaOH at 80−95 °C. In addition, the advantage of good solvent processability and convenient scalability of the reaction process generates considerable interest in these polymers as commercial standard AEM candidates. AEM fuel cell and electrolyzer tests of some of the developed polymer membranes showed excellent performance, suggesting that this new class of HCPs opens a new avenue to electrochemical devices with real-world applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Metal–Organic Framework-Based Microfluidic Impedance Sensor Platform for Ultrasensitive Detection of Perfluorooctanesulfonate

The growing global concerns to public health from human exposure to perfluorooctanesulfonate (PFOS) requires rapid, sensitive, in-situ detection where current, state-of-the-art techniques are yet to adequately meet sensitivity and selectivity standards of the real-world. This work presents, for the first time, a synergistic approach for the targeted affinity-based capture of PFOS using a porous sorbent probe that enhances detection sensitivity by embedding it on a microfluidic conductive platform. This novel sorbent-containing platform functions as an electrochemical sensor to directly measure PFOS concentration through a proportional change in electrical response (increase in impedance). The extremely high surface area and pore volume of mesoporous metal-organic framework (MOF) Cr-MIL-101 is used as the probe for targeted PFOS capture based on the affinity of the chromium center towards both the fluorine tail groups as well as the sulfonate functionalities as demonstrated by spectroscopic (NMR and XPS) and microscopic (TEM) studies. Answering the need for an ultrasensitive PFOS detection technique, we are embedding these MOF capture probes inside a microfluidic channel, sandwiched between interdigitated microelectrodes (IDµE). The nanoporous geometry increases the signal to noise ratio of interdigitated microelectrodes tremendously increasing sensitivity; this in combination with the ability of the capture probes to interact with the PFOS at the molecular level and effectively transduce that response electrochemically has allowed us achieve a PFOS detection limit of 0.5 ng/L, which is unprecedented for in-situ analytical PFOS sensors and even comparable to quantification limits achieved using state-of-the-art ex situ techniques.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The SRT reconstruction algorithm for semiquantification in PET imaging

Purpose: The spline reconstruction technique (SRT) is a new, fast algorithm based on a novel numerical implementation of an analytic representation of the inverse Radon transform. The mathematical details of this algorithm and comparisons with filtered backprojection were presented earlier in the literature. In this study, the authors present a comparison between SRT and the ordered-subsets expectation–maximization (OSEM) algorithm for determining contrast and semiquantitative indices of {sup 18}F-FDG uptake. Methods: The authors implemented SRT in the software for tomographic image reconstruction (STIR) open-source platform and evaluated this technique using simulated and real sinograms obtained from the GE Discovery ST positron emission tomography/computer tomography scanner. All simulations and reconstructions were performed in STIR. For OSEM, the authors used the clinical protocol of their scanner, namely, 21 subsets and two iterations. The authors also examined images at one, four, six, and ten iterations. For the simulation studies, the authors analyzed an image-quality phantom with cold and hot lesions. Two different versions of the phantom were employed at two different hot-sphere lesion-to-background ratios (LBRs), namely, 2:1 and 4:1. For each noiseless sinogram, 20 Poisson realizations were created at five different noise levels. In addition to making visual comparisons of the reconstructed images, the authors determined contrast and bias as a function of the background image roughness (IR). For the real-data studies, sinograms of an image-quality phantom simulating the human torso were employed. The authors determined contrast and LBR as a function of the background IR. Finally, the authors present plots of contrast as a function of IR after smoothing each reconstructed image with Gaussian filters of six different sizes. Statistical significance was determined by employing the Wilcoxon rank-sum test. Results: In both simulated and real studies, SRT exhibits higher contrast and lower bias than OSEM at the cold lesions. This improvement is achieved at the expense of increasing the noise in the reconstructed images. For the hot lesions, SRT exhibits a small improvement in contrast and LBR over OSEM with 21 subsets and two iterations; however, this improvement is not statistically significant. As the number of iterations increases, the performance of OSEM improves over SRT but again without statistical significance. The curves of contrast and LBR as a function of IR after Gaussian blurring indicate that the advantage of SRT in the cold regions is maintained even after decreasing the noise level by Gaussian blurring. Conclusions: SRT, at the expense of slightly increased noise in the reconstructed images, reconstructs images of higher contrast and lower bias than the clinical protocol of OSEM. This improvement is particularly evident for images involving cold regions. Thus, it appears that SRT should be particularly useful for the quantification of low-count and cold regions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Stochastic Resolution of Identity for Real-Time Second-Order Green’s Function: Ionization Potential and Quasi-Particle Spectrum

Here, we develop a stochastic resolution of identity approach to the real-time second-order Green's function (real-time sRI-GF2) theory, extending our recent work for imaginary-time Matsubara Green's function [ Takeshita et al. J. Chem. Phys. 2019 , 151 , 044114 ]. The approach provides a framework to obtain the quasi-particle spectra across a wide range of frequencies and predicts ionization potentials and electron affinities. To assess the accuracy of the real-time sRI-GF2, we study a series of molecules and compare our results to experiments as well as to a many-body perturbation approach based on the GW approximation, where we find that the real-time sRI-GF2 is as accurate as self-consistent GW. The stochastic formulation reduces the formal computatinal scaling from O(N e 5 ) down to O(N e 3 ) where N e is the number of electrons. Finally, this is illustrated for a chain of hydrogen dimers, where we observe a slightly lower than cubic scaling for systems containing up to N e ≈ 1000 electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Assessment of Condition Monitoring Methods and Technologies for Inservice Inspection and Testing of Nuclear Power Plant Components

This report was prepared for the U.S. Nuclear Regulatory Commission (NRC) to explore the application of advanced technologies toward meeting the current and future regulatory requirements for maintenance and condition monitoring of structures, systems, and components. The advanced technologies considered in this work are advanced sensors and instrumentation, data analytics, machine learning and artificial intelligence (ML/AI), physics-based models, and digital twins (DT). The interest in the application of advanced technologies for condition monitoring in nuclear power plants continues to grow, and current and future licensees are expected to implement advanced technologies as part of their inservice inspection (ISI) and inservice testing (IST) programs. This report delineates the outcomes of an exploratory investigation into the implementation of advanced condition monitoring technologies to address ISI and IST requirements. A thorough review was conducted of the existing regulatory requirements for ISI and IST, along with an analysis of associated industry practices. Additionally, a state-of-the-art assessment was performed on advanced condition monitoring technologies frequently employed in non-nuclear sectors. This research incorporated two nuclear-specific case studies to illustrate the application of these technologies within the current nuclear fleet. The report provides an exhaustive discussion on the technical challenges, considerations, and opportunities associated with the deployment of advanced condition monitoring technologies. The following are key considerations in the application of advanced technologies for the ISI and IST of nuclear power plant components: • Developing adequate verification and validation procedures to confirm the functional and non-functional requirements, • Developing technical capabilities to conduct real-time asset condition monitoring, • Establishing guidance and protocol for modeling and simulation tools to continuously meet regulatory requirements, • Addressing trustworthiness, explainability, and interpretability of ML/AI methods, • Evaluating maintenance activities to maintain an adequate safety margin and avoid undesirable conditions, • Establishing cybersecure condition monitoring programs associated with a computer-based software system, and • Establishing standardized evaluation metrics for advanced condition monitoring programs. Interest in the use of advanced technologies for condition monitoring in ISI and IST programs continues to grow, and the technology is expected to experience rapid and wide industry adoption in the near future. Adoption of advanced technologies for condition monitoring could have novel and unique impacts on regulatory activities associated with ISI and IST programs. The NRC is continuing to explore the regulatory aspects of advanced technologies as part of ISI and IST programs by pursuing additional research in this technical area.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Dynamic Manipulation in Piezoresponse Force Microscopy: Creating Nonequilibrium Phases with Large Electromechanical Response

We discuss how domain walls and topological defects in ferroelectric materials have emerged as a powerful tool for functional electronic devices including memory and logic. Similarly, wall interactions and dynamics underpin a broad range of mesoscale phenomena ranging from giant electromechanical responses to memory effects. Exploring the functionalities of individual domain walls, their interactions, and controlled modifications of the domain structures is crucial for applications and fundamental physical studies. However, the dynamic nature of these features severely limits studies of their local physics since application of local biases or pressures in piezoresponse force microscopy induce wall displacement as a primary response. Here, we introduce an approach for the control and modification of domain structures based on automated experimentation, whereby real-space image-based feedback is used to control the tip bias during ferroelectric switching, allowing for modification routes conditioned on domain states under the tip. This automated experiment approach is demonstrated for the exploration of domain wall dynamics and creation of metastable phases with large electromechanical response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Improved Infrared Optical Constants from Pressed Pellets: II. Ellipsometric n and k Values for Ammonium Sulfate with Variability Analysis

Infrared spectral imaging is facilitated via the comparison of spectra recorded in situ to a databank of actual or synthetic infrared reflectance spectra. It has recently been shown that reference spectra corresponding to the many different morphological forms of the same chemical can be generated synthetically using the imaginary, k, and real, n, components of the complex refractive index, n~ = n + ik. One method to obtain the n and k vectors is infrared ellipsometry, which measures the changes in amplitude, tan ?, and phase, ?, of polarized light reflected from the sample both as a function of wavenumber and angle of incidence. The method requires specularly reflected light so best results are usually obtained with polished planar samples of large surface area. Due to the difficulties of obtaining such samples, however, we investigate the possibility of pressing powders of neat materials and obtaining the corresponding optical constants from the pellets. In this paper, variability in the sample pellet and preparation method is investigated, as is variability in the fitting procedure for the derived optical constants. The n/k vectors are derived from the measured ellipsometric parameters, tan ? and ?, as they are fit by an oscillator model which yield n(?) and k(?) vectors as a function of wavenumber, ?. Construction of the oscillator model is not automatic and depends on significant input from the analyst as well as the sample’s physical characteristics. For the pellet pressing, the experimental variability was found to be minimized for size-selected powdered samples as gauged by the minimal variance in ? and ? for three different pellets; similarly, the analytical precision for multiple measurements of the same pellet was also quite good, suggesting that a pressed pellet is a viable sample preparation method. The greatest variability came in the analytic fitting procedure with differences up to 20% arising from four different fits to the same data set. The final ellipsometric n/k data are compared to literature values obtained from crystalline (NH4)2SO4 samples as well as single-angle reflectance measurements that also used pressed pellets. Comparison with the previous literature values shows generally good agreement although higher k-values are observed for the independent sets of data derived from pressed pellets. These data are suggested as an improved set of optical constants for (NH4)2SO4.

optical constants, ellipsometry, ammonium sulfate,↗
DOE OSTI2016

Editorial: Biomass Modification, Characterization, and Process Monitoring Analytics to Support Biofuel and Biomaterial Production

This Frontiers Research Topic journeys through various challenges facing researchers seeking to develop fuels and products derived from lignocellulosic biomass. These challenges include: the rapid quantification of plant cell wall chemistry, enabling yields of potential monomeric sugars to be assessed, identification of plants possessing ideal trait that can be brought to the forefront of research efforts; once the native plant chemistry is known, how can yields be improved by chemically or genetically altering plant cell walls to reduce recalcitrance; does genetic modification of plants to increase accessibility to saccharification enzymes hinder the plant’s growth and/or function; are the innovative methods identified by researchers cost-effective and scalable to a commercial level? These topics are a sampling of the obstacles researchers combat when nominating a specific plant for downstream applications or implementing new deconstruction, genetic, or measurement strategies. How well can different plants can be broken down into useful, downstream precursor molecules? Efforts to develop a lucid picture of the chemical composition of abundant, diverse plants being explored as potential starting feedstocks has resulted in the evolution of high-throughput techniques that permit many more samples to be screened in much shorter periods of time. Advances in thermochemical and spectroscopic techniques have enabled the screening of thousands of plants for different phenotypes, such as cell-wall composition and monomeric sugar release. Some instrumental methods have been coupled with multivariate analysis, providing elegant chemometric predictive models enabling the accelerated identification of potential feedstocks. Rapid instrumental techniques have been developed for real-time monitoring of diverse processes, such as the efficacy of specific pretreatment strategies, or downstream products, such as biofuels and biomaterials. Real-time process monitoring techniques are needed for all stages of the feedstocks-to-biofuels conversion process to maximize efficiency and lower costs by monitoring and optimizing performance. These approaches allow researchers to adjust experimental conditions during, rather than at the conclusion, of processes, thereby decreasing overhead expenses.

09 BIOMASS FUELS↗
DOE OSTI2020

Local Atomic Structure in Photo-isomerized Ruthenium Sulfur Dioxide Complexes Revealed by Pair Distribution Function Analysis

SO 2 linkage photoisomerization in crystalline ruthenium-based complexes has demonstrated nanophotonic phenomena such as optical switching and nano-optomechanical transduction. Molecular insights into these materials have been explored largely via the characterization of their photoinduced crystal structures via in situ single-crystal X-ray diffraction, known as photocrystallography. Photoinduced molecular disorder is present, which photocrystallography can model to the extent that it is confined within the periodic boundary of a unit cell. However, non-periodic molecular disorder is suspected to exist as well. In situ total scattering experiments were therefore carried out on finely powdered crystals of four ruthenium-sulfur dioxide complexes. Data were modeled using light-minus-dark' difference pair distribution function analysis, which afforded photoinduced structural changes exclusively. This revealed structural features that were first compared against models of photoinduced crystal structures known a priori from photocrystallography. Furthermore, statistical inference was then employed, which evidenced generally good agreement between the total scattering data and the photocrystallographic models, while revealing real differences that are indicative of a structure with only a short-range order. Overall, our findings demonstrate that in situ light-induced total scattering experiments on finely powdered crystals are able to reveal the photoinduced structure. Overall, the evidence suggests that such structure could include a short-range order as well as photocrystallographic content. Our demonstration experiment offers a pathway to develop studies that capture the short-range order in linkage photoisomers, while we have outlined the procedure for testing the validity of associated structural models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Gaussian variational ansatz in the problem of anomalous sea waves: Comparison with direct numerical simulation

The nonlinear dynamics of an obliquely oriented wave packet on a sea surface is analyzed analytically and numerically for various initial parameters of the packet in relation to the problem of the so-called rogue waves. Within the Gaussian variational ansatz applied to the corresponding (1+2)-dimensional hyperbolic nonlinear Schrödinger equation (NLSE), a simplified Lagrangian system of differential equations is derived that describes the evolution of the coefficients of the real and imaginary quadratic forms appearing in the Gaussian. This model provides a semi-quantitative description of the process of nonlinear spatiotemporal focusing, which is one of the most probable mechanisms of rogue wave formation in random wave fields. The system of equations is integrated in quadratures, which allows one to better understand the qualitative differences between linear and nonlinear focusing regimes of a wave packet. Predictions of the Gaussian model are compared with the results of direct numerical simulation of fully nonlinear long-crested waves.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Sulfate-Controlled Heterogeneous CaCO 3 Nucleation and Its Non-linear Interfacial Energy Evolution

Unveiling the effects of an environmental abundant anion “sulfate” on the formation of calcium carbonate (CaCO 3 ) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate–CaCO 3 interactions at the explicit first step of CaCO 3 formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO 3 nucleation is monitored in real time as a function of sulfate concentrations (0–10 mM Na 2 SO 4 ) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO 3 nucleation rate, causing a 120% increase in the CaCO 3 nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO 3 and finds a non-linear trend, suggesting that CaCO 3 heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO 3 interfacial energies, a key step toward achieving natural and engineered controls on CaCO 3 nucleation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Coexistence of Multilayered Phases of Confined Water: The Importance of Flexible Confining Surfaces

Flexible nanoscale confinement is critical to understanding the role that bending fluctuations play on biological processes where soft interfaces are ubiquitous or to exploit confinement effects in engineered systems where inherently flexible 2D materials are pervasively employed. Here, using molecular dynamics simulations, we compare the phase behavior of water confined between flexible and rigid graphene sheets as a function of the in-plane density, ρ2D. We find that both cases show commensurate mono-, bi-, and trilayered states; however, the water phase in those states and the transitions between them are qualitatively different for the rigid and flexible cases. The rigid systems exhibit discontinuous transitions between an ( n )-layer and an ( n +1)-layer state at particular values of ρ2D, whereas under flexible confinement, the graphene sheets bend to accommodate an ( n )-layer and an (n+1)-layer state coexisting in equilibrium at the same density. We show that the flexible walls introduce a very different sequence of ice phases and their phase coexistence with vapor and liquid phases than that observed with rigid walls. We discuss the applicability of these results to real experimental systems to shed light on the role of flexible confinement and its interplay with commensurability effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

Grubbs 3rd-generation (G3) pre-catalyst-initiated ring-opening metathesis polymerization (ROMP) remains an indispensable tool in the polymer chemist's toolbox. Tricyclononenes (TCN) and tricyclononadienes (TCND) represent under-explored classes of monomers for ROMP that have the potential to both advance fundamental knowledge (e.g., structure-polymerization kinetics relationships) and serve as practical tools for the polymer chemist (e.g., post-polymerization functionalization). In this work, a library of TCN and TCND imides, monoesters, and diesters, along with their exo-norbornene counterparts, were synthesized to compare their behaviors in G3-initiated ROMP. Real-time 1 H NMR was used to study their polymerization kinetics; propagation rates ( k p ) were extracted for each monomer. To understand the relationships between monomer structure and ROMP propagation rates, density functional theory methods were used to calculate a variety of electronic and steric parameters for each monomer. While electronic parameters (e.g., HOMO energy levels) correlated positively with the measured k p values, steric parameters generally gave improved correlations, which indicates that monomer size and shape are better predictors for k p than electronic parameters for this data set. Furthermore, the TCND diester—which contains an electron-deficient cyclobutene that is resistant to ROMP—and its polymer p(TCND) are shown to be highly reactive toward DBU-catalyzed conjugate addition reactions with thiols, providing a protecting- and activating-group free strategy for post-polymerization modification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Thermodynamic properties of “near-perfect” gas

When applied thermodynamics requires simple representations of thermodynamic quantities, one often finds quantities such as pressure and the thermal energy density expressed as a monomial linear product of density and temperature power laws. This is a simple generalization of the product of density and temperature used for the perfect gas that admits a broader range of thermodynamic behavior into analytic fluid calculations or provides an analytic form that is readily fit to tabulated equation-of-state data for an arbitrary material. This paper reviews the thermodynamic properties of this generalized perfect-gas model, treating it as a class of “near-perfect-gas” models that are defined and unified here, for the first time, through a shared Helmholtz free energy. This generalization from perfect to near-perfect-gas models preserves some perfect-gas properties (e.g., constant adiabatic exponents) but not others (e.g., constant specific heats) and is constrained by thermodynamic consistency. It is important to be aware of the properties of this class of near-perfect-gas models when using them as surrogates for real nonperfect materials that may have properties that cannot be captured by near-perfect-gas models.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Representative Atmospheric Plume Development for Elevated Releases

An atmospheric explosion of a low-yield nuclear device will produce a large number of radioactive isotopes, some of which can be measured with airborne detection systems. However, properly equipped aircraft may not arrive in the region where an explosion occurred for a number of hours after the event. Atmospheric conditions will have caused the radioactive plume to move and diffuse before the aircraft arrives. The science behind predicting atmospheric plume movement has advanced enough that the location of the maximum concentrations in the plume can be determined reasonably accurately in real time, or near real time. Given the assumption that an aircraft can follow a plume, this study addresses the amount of atmospheric dilution expected to occur in a representative plume as a function of time past the release event. The approach models atmospheric transport of hypothetical releases from a single location for every day in a year using the publically available HYSPLIT code. The effective dilution factors for the point of maximum concentration in an elevated plume based on a release of a non-decaying, non-depositing tracer can vary by orders of magnitude depending on the day of the release, even for the same number of hours after the release event. However, the median of the dilution factors based on releases for 365 consecutive days at one site follows a power law relationship in time, as shown in Figure S-1. The relationship is good enough to provide a general rule of thumb for estimating typical future dilution factors in a plume starting at the same point. However, the coefficients of the power law function may vary for different release point locations. Radioactive decay causes the effective dilution factors to decrease more quickly with the time past the release event than the dilution factors based on a non-decaying tracer. An analytical expression for the dilution factors of isotopes with different half-lives can be developed given the power law expression for the non-decaying tracer. If the power-law equation for the median dilution factor, Df, based on a non-decaying tracer has the general form Df=a(×t)^(-b) for time t after the release event, then the equation has the form Df=e^(-λt)×a×t^(-b) for a radioactive isotope, where λ is the decay constant for the isotope.

54 ENVIRONMENTAL SCIENCES↗