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DOE OSTI2022

Potential for Evaporation and In Situ Reaction of Organic Compounds in Hanford Supplemental LAW

The presence of regulated organic species in Hanford nuclear tank waste is assessed in this report, along with fate of the organics and possible evaporative treatment. A narrowed list of regulated organic species of concern is developed based upon published analyses, chemical properties like aqueous solubility, and chemical reactivity under alkaline conditions. Published analyses include tank headspace and liquid samples, review of chemical reagents formerly used at Hanford, and the Tank Waste Information Network System (TWINS). This work supports possible stabilization of Hanford Supplemental Low Activity Waste (SLAW) by grouting.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Potential for Evaporation and In Situ Reaction of Organic Compounds in Hanford Supplemental LAW

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Persistent Homology Metrics Reveal Quantum Fluctuations and Reactive Atoms in Path Integral Dynamics

Nuclear quantum effects (NQEs) are known to impact a number of features associated with chemical reactivity and physicochemical properties, particularly for light atoms and at low temperatures. In the imaginary time path integral formalism, each atom is mapped onto a “ring polymer” whose spread is related to the quantum mechanical uncertainty in the particle’s position, i.e., its thermal wavelength. A number of metrics have previously been used to investigate and characterize this spread and explain effects arising from quantum delocalization, zero-point energy, and tunneling. Many of these shape metrics consider just the instantaneous structure of the ring polymers. However, given the significant interest in methods such as centroid molecular dynamics and ring polymer molecular dynamics that link the molecular dynamics of these ring polymers to real time properties, there exists significant opportunity to exploit metrics that also allow for the study of the fluctuations of the atom delocalization in time. Here we consider the ring polymer delocalization from the perspective of computational topology, specifically persistent homology, which describes the 3-dimensional arrangement of point cloud data, (i.e. atomic positions). We employ the Betti sequence probability distribution to define the ensemble of shapes adopted by the ring polymer. The Wasserstein distances of Betti sequences adjacent in time are used to characterize fluctuations in shape, where the Fourier transform and associated principal components provides added information differentiating atoms with different NQEs based on their dynamic properties. We demonstrate this methodology on two representative systems, a glassy system consisting of two atom types with dramatically different de Broglie thermal wavelengths, and ab initio molecular dynamics simulation of an aqueous 4 M HCl solution where the H-atoms are differentiated based on their participation in proton transfer reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1976

Apollo experience report: Detection and minimization of ignition hazards from water/glycol contamination of silver-clad electrical circuitry

The potential flammability hazard when a water/glycol solution contacts defectively insulated silver-clad copper circuitry or electrical components carrying a direct current is described. The chemical reactions and means for detecting them are explained. Methods for detecting and cleaning contaminated areas and the use of inhibitors to arrest chemical reactivity are also explained. Preventive measures to minimize hazards are given. Photomicrographs of the chemical reactions occurring on silver clad wires are also included.

Downs, W. R.↗

NASA NTRS2018

GMI-IPS: Python Processing Software for Aircraft Campaigns

NASA's Atmospheric Tomography Mission (ATom) seeks to understand the impact of anthropogenic air pollution on gases in the Earth's atmosphere. Four flight campaigns are being deployed on a seasonal basis to establish a continuous global-scale data set intended to improve the representation of chemically reactive gases in global atmospheric chemistry models. The Global Modeling Initiative (GMI), is creating chemical transport simulations on a global scale for each of the ATom flight campaigns. To meet the computational demands required to translate the GMI simulation data to grids associated with the flights from the ATom campaigns, the GMI ICARTT Processing Software (GMI-IPS) has been developed and is providing key functionality for data processing and analysis in this ongoing effort. The GMI-IPS is written in Python and provides computational kernels for data interpolation and visualization tasks on GMI simulation data. A key feature of the GMI-IPS, is its ability to read ICARTT files, a text-based file format for airborne instrument data, and extract the required flight information that defines regional and temporal grid parameters associated with an ATom flight. Perhaps most importantly, the GMI-IPS creates ICARTT files containing GMI simulated data, which are used in collaboration with ATom instrument teams and other modeling groups. The initial main task of the GMI-IPS is to interpolate GMI model data to the finer temporal resolution (1-10 seconds) of a given flight. The model data includes basic fields such as temperature and pressure, but the main focus of this effort is to provide species concentrations of chemical gases for ATom flights. The software, which uses parallel computation techniques for data intensive tasks, linearly interpolates each of the model fields to the time resolution of the flight. The temporally interpolated data is then saved to disk, and is used to create additional derived quantities. In order to translate the GMI model data to the spatial grid of the flight path as defined by the pressure, latitude, and longitude points at each flight time record, a weighted average is then calculated from the nearest neighbors in two dimensions (latitude, longitude). Using SciPya's Regular Grid Interpolator, interpolation functions are generated for the GMI model grid and the calculated weighted averages. The flight path points are then extracted from the ATom ICARTT instrument file, and are sent to the multi-dimensional interpolating functions to generate GMI field quantities along the spatial path of the flight. The interpolated field quantities are then written to a ICARTT data file, which is stored for further manipulation. The GMI-IPS is aware of a generic ATom ICARTT header format, containing basic information for all flight campaigns. The GMI-IPS includes logic to edit metadata for the derived field quantities, as well as modify the generic header data such as processing dates and associated instrument files. The ICARTT interpolated data is then appended to the modified header data, and the ICARTT processing is complete for the given flight and ready for collaboration. The output ICARTT data adheres to the ICARTT file format standards V1.1. The visualization component of the GMI-IPS uses Matplotlib extensively and has several functions ranging in complexity. First, it creates a model background curtain for the flight (time versus model eta levels) with the interpolated flight data superimposed on the curtain. Secondly, it creates a time-series plot of the interpolated flight data. Lastly, the visualization component creates averaged 2D model slices (longitude versus latitude) with overlaid flight track circles at key pressure levels. The GMI-IPS consists of a handful of classes and supporting functionality that have been generalized to be compatible with any ICARTT file that adheres to the base class definition. The base class represents a generic ICARTT entry, only defining a single time entry and 3D spatial positioning parameters. Other classes inherit from this base class; several classes for input ICARTT instrument files, which contain the necessary flight positioning information as a basis for data processing, as well as other classes for output ICARTT files, which contain the interpolated model data. Utility classes provide functionality for routine procedures such as: comparing field names among ICARTT files, reading ICARTT entries from a data file and storing them in data structures, and returning a reduced spatial grid based on a collection of ICARTT entries. Although the GMI-IPS is compatible with GMI model data, it can be adapted with reasonable effort for any simulation that creates Hierarchical Data Format (HDF) files. The same can be said of its adaptability to ICARTT files outside of the context of the ATom mission. The GMI-IPS contains just under 30,000 lines of code, eight classes, and a dozen drivers and utility programs. It is maintained with GIT source code management and has been used to deliver processed GMI model data for the ATom campaigns that have taken place to date.

Damon, M. R.↗

DOE OSTI2023

Enhancing reactivity of SiO + ions by controlled excitation to extreme rotational states

Optical pumping of molecules provides unique opportunities for control of chemical reactions at a wide range of rotational energies. This work reports a chemical reaction with extreme rotational excitation of a reactant and its kinetic characterization. We investigate the chemical reactivity for the hydrogen abstraction reaction SiO + + H 2 → SiOH + + H in an ion trap. The SiO + cations are prepared in a narrow rotational state distribution, including super-rotor states with rotational quantum number ( j ) as high as 170, using a broad-band optical pumping method. We show that the super-rotor states of SiO + substantially enhance the reaction rate, a trend reproduced by complementary theoretical studies. We reveal the mechanism for the rotational enhancement of the reactivity to be a strong coupling of the SiO + rotational mode with the reaction coordinate at the transition state on the dominant dynamical pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Theoretical Advances in Polariton Chemistry and Molecular Cavity Quantum Electrodynamics

When molecules are coupled to an optical cavity, new light–matter hybrid states, so-called polaritons, are formed due to quantum light–matter interactions. With the experimental demonstrations of modifying chemical reactivities by forming polaritons under strong light–matter interactions, theorists have been encouraged to develop new methods to simulate these systems and discover new strategies to tune and control reactions. This review summarizes some of these exciting theoretical advances in polariton chemistry, in methods ranging from the fundamental framework to computational techniques and applications spanning from photochemistry to vibrational strong coupling. Even though the theory of quantum light–matter interactions goes back to the midtwentieth century, the gaps in the knowledge of molecular quantum electrodynamics (QED) have only recently been filled. We review recent advances made in resolving gauge ambiguities, the correct form of different QED Hamiltonians under different gauges, and their connections to various quantum optics models. Then, we review recently developed ab initio QED approaches which can accurately describe polariton states in a realistic molecule–cavity hybrid system. We then discuss applications using these method advancements. We review advancements in polariton photochemistry where the cavity is made resonant to electronic transitions to control molecular nonadiabatic excited state dynamics and enable new photochemical reactivities. When the cavity resonance is tuned to the molecular vibrations instead, ground-state chemical reaction modifications have been demonstrated experimentally, though its mechanistic principle remains unclear. We present some recent theoretical progress in resolving this mystery. Finally, we review the recent advances in understanding the collective coupling regime between light and matter, where many molecules can collectively couple to a single cavity mode or many cavity modes. We also lay out the current challenges in theory to explain the observed experimental results. We hope that this review will serve as a useful document for anyone who wants to become familiar with the context of polariton chemistry and molecular cavity QED and thus significantly benefit the entire community.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Engineered disorder in CO 2 photocatalysis

Light harvesting, separation of charge carriers, and surface reactions are three fundamental steps that are essential for an efficient photocatalyst. Here we show that these steps in the TiO 2 can be boosted simultaneously by disorder engineering. A solid-state reduction reaction between sodium and TiO 2 forms a core-shell c-TiO 2 @a-TiO 2-x (OH) y heterostructure, comprised of HO-Ti-[O]-Ti surface frustrated Lewis pairs (SFLPs) embedded in an amorphous shell surrounding a crystalline core, which enables a new genre of chemical reactivity. Specifically, these SFLPs heterolytically dissociate dihydrogen at room temperature to form charge-balancing protonated hydroxyl groups and hydrides at unsaturated titanium surface sites, which display high reactivity towards CO 2 reduction. This crystalline-amorphous heterostructure also boosts light absorption, charge carrier separation and transfer to SFLPs, while prolonged carrier lifetimes and photothermal heat generation further enhance reactivity. The collective results of this study motivate a general approach for catalytically generating sustainable chemicals and fuels through engineered disorder in heterogeneous CO 2 photocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

MODELING AND PARAMETRIC STUDY OF END-GAS AUTOIGNITION TO ALLOW THE REALIZATION OF ULTRA-LOW EMISSIONS, HIGH-EFFICIENCY HEAVY-DUTY SPARK-IGNITED NATURAL GAS ENGINES

Engine knock and misfire are barriers to pathways leading to high-efficiency Spark-Ignited (SI) Natural Gas (NG) engines. The general tendency to knock is highly dependent on engine operating conditions and the fuel reactivity. The problem is further complicated by the low emission limits and the wide range of chemical reactivity in pipeline-quality natural gas. Depending on the region and the source of the natural gas, its reactivity, described by its Methane Number (MN), which is analogous to the Octane Number for liquid SI fuels, can span from 65 to 95. In order to realize diesel-like efficiencies, SI NG engines must be designed to operate at high Brake Mean Effective Pressures (BMEP), near or beyond knock limits, over a wide range of fuel reactivity. This requires a deep understanding of the combustion-engine interactions pertaining to flame propagation and End-Gas Autoignition (EGAI), i.e., the autoignition of the unburned gas (end gas) ahead of the flame front. However, EGAI, if controlled, provides an opportunity to increase SI NG engine efficiency by increasing the combustion rate and the total fraction of burned fuel, mitigating the effects of the slow flame speeds characteristic of natural gas fuels, which generally reduce BMEP and increase unburned hydrocarbon emissions. For this reason, to realize diesel-like efficiencies and ultra-low emissions on SI NG engines, this work proposes the study of the main parameters influencing the modeling and prediction of NG EGAI to allow for its control. In this work, a novel EGAI detection and onset determination method was developed to reliably quantify EGAI for data analysis and engine control. The new method allowed the prediction of EGAI on SI NG engines without the need to use engine- and operating-condition-dependent thresholds and reduced the error in quantifying the fraction of the total energy released by the EGAI event by up to 40%pts. One- and three-dimensional engine models were then developed to study the engine/fuel interactions that lead to NG EGAI and its performance benefits. These models, although having decent agreement with experimental data, showed the need to account for NOx chemistry when predicting NG EGAI due to a consistently later prediction of the EGAI onset (~1.65 crank-angle degrees) and thus, a new reduced chemical mechanism for real NG fuels was developed containing NOx chemistry. The new reduced mechanism improved the EGAI onset prediction agreement to within ±0.5 crank-angle degrees and decreased simulation time during combustion by nearly 50% when using the further reduced AREIS50NOx chemical mechanism. These models were then used to study the role of NG composition on EGAI, evaluate the engine/fuel interactions leading to NG EGAI, and perform engine optimization while leveraging EGAI to increase thermal efficiency. Piston design optimization combined with a Controlled EGAI (C-EGAI) combustion mode allowed a Heavy-Duty (HD) SI NG engine to operate at diesel-like efficiencies, i.e., Brake Thermal Efficiency (BTE) ≥44%. Experimental and modeling data analysis revealed that earlier and faster heat release increases combustion efficiency by an average of 1%pts, increases work transferred to the piston resulting in a decrease in exhaust losses by 50% depending on the engine operating condition while slightly increasing heat losses. Finally, the simulation results revealed an opportunity to further enhance the BTE (up to 50%) by enabling C-EGAI combustion at leaner conditions, λ=1.4-1.6.

Bestel, Diego Bernardi↗

DOE OSTI2022

A perspective on iron (Fe) in the atmosphere: air quality, climate, and the ocean

As scientists engage in research motivated by climate change and the impacts of pollution on air, water, and human health, we increasingly recognize the need for the scientific community to improve communication and knowledge exchange across disciplines to address pressing and outstanding research questions holistically. Our professional paths have crossed because our research activities focus on the chemical reactivity of Fe-containing minerals in air and water, and at the air-sea interface. (Photo)chemical reactions driven by Fe can take place at the surface of the particles/droplets or within the condensed phase. The extent and rates of these reactions are influenced by water content and biogeochemical activity ubiquitous in these systems. One of these reactions is the production of reactive oxygen species (ROS) that cause damage to respiratory organs. Another is that the reactivity of Fe and organics in aerosol particles alter surficial physicochemical properties that impact aerosol-radiation and aerosol–cloud interactions. Also, upon deposition, aerosol particles influence ocean biogeochemical processes because micronutrients such as Fe or toxic elements such as copper become bioavailable. We provide a perspective on these topics and future research directions on the reactivity of Fe in atmospheric aerosol systems, from sources to short- and long-term impacts at the sinks with emphasis on needs to enhance the predictive power of atmospheric and ocean models.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

THE EFFECT OF FUEL REACTIVITY AND EXHAUST GAS RECIRCULATION ON KNOCK PROPENSITY OF NATURAL GAS

The development of high efficiency, spark ignited natural gas engines is currently limited by engine knock at high compression ratio/elevated boost pressures and misfire at lean conditions/high exhaust gas recirculation (EGR) levels. The knock and misfire limits are further confounded by the wide variety in fuel reactivity observed in “pipeline quality” natural gas. In this study, a rapid compression machine was used to characterize the effects of EGR and variation in natural gas fuel reactivity on the homogeneous ignition delay, flame propagation rate, and end- gas autoignition propensity for stoichiometric natural gas/oxidizer/EGR blends. A reduced chemical kinetic mechanism was also developed to accurately model the homogeneous ignition delays measured in the Colorado State University rapid compression machine (CSU RCM). Pipeline quality natural gas with a range of chemical reactivity (68 < Methane Number < 95) was simulated using mixtures of CH4, C2H6, and C3H8. Exhaust gas recirculation gases were simulated with mixtures of Ar, CO2, CO, and NO at substitution rates of 0 to 30 mass percent. Ignition delay period under homogeneous autoignition conditions was measured at compressed pressures of 30.2 to 34.0 bar and compressed temperatures of 667 to 980 K. End-gas autoignition fraction and flame propagation rate were measured by initiating a laser spark in the center of the combustion chamber, after compression, at pressures of 30.7 to 32.7 bar and temperatures of 751 to 795 K. The results indicate that both fuel reactivity and the presence of reactive species (NO and CO) in the exhaust gas recirculation have a strong impact on end-gas autoignition fraction. A chemical kinetic mechanism was developed to predict homogeneous ignition delays for pipeline quality natural gas in a pressure and temperature range of 1-100 bar and 500-1000 K respectively. This mechanism accurately predicted measured homogeneous ignition delay in the RCM with a total average relative error of 11.0%.

Mohr, Jeffrey↗

DOE OSTI2022

Impact of Fuel Properties on the Combustion of Late Post Injections used for Aftertreatment Thermal Management

Typical calibration for catalyst thermal management for compression-ignition engines involves delaying the post-injection into the expansion stroke. Reduced work extraction due to the late heat release event is used to increase the exhaust gas temperature to shorten the time associated with reaching optimal temperatures for aftertreatment systems. Shorter catalyst heat-up time can simultaneously reduce tail-pipe emissions and the typical fuel penalties associated with this mode of operation. In this study, the effects of volatility, reactivity, and oxygen content of the fuel on combustion stability and emissions were studied in a light-duty single-cylinder research engine. Blends of iso-octane/ n-heptane and farnesane/ 2,2,4,4,6,8,8-heptamethylnonane were used to study the impacts of volatility and reactivity. At constant reactivity, little to no variation in combustion performance was observed due to differences in volatility. On the other hand, increased reactivity improved combustion stability and efficiency at late injection timings (+24 CAD). The combined effect of increase in chemical reactivity and oxygen content was analysed by comparing the baseline #2 diesel operation with two blends of mono-ethers and #2 diesel to achieve cetane numbers (CNs) of 45 and 55, and a pure blend of mono-ether components with CN > 100. Fuels with higher reactivity and oxygen content were found to reduce engine-out hydrocarbon and carbon mono-oxide emissions while also achieving stable combustion at post-injection timings later than those achievable with diesel fuel. The pure ether-blend had the latest achievable post-injection timing (≥+26 CAD) while still maintaining stable combustion. At similar combustion stability, the pure ether blend was found to have 2.8% higher combustion efficiency and 4.3% higher thermal efficiency than the baseline diesel. The ether-diesel blends at CN45 and CN55 were found to have 1.8% higher combustion efficiency than baseline diesel. The results demonstrate that fuels with increased reactivity can increase combustion efficiency, reducing carbon monoxide and hydrocarbon emissions, while maintaining similar exhaust temperature and combustion stability compared to baseline diesel. Further greenhouse gas benefits can also be realized as the mono-ether bioblendstocks show potential for >50% reduction in greenhouse gas emissions relative to diesel fuel based on their production method.

99 GENERAL AND MISCELLANEOUS↗

NASA NTRS2000

Evidence that the reactivity of the martian soil is due to superoxide ions

The Viking Landers were unable to detect evidence of life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules. This reactivity was attributed to the presence of one or more as-yet-unidentified inorganic superoxides or peroxides in the martian soil. Using electron paramagnetic resonance spectroscopy, we show that superoxide radical ions (O2-) form directly on Mars-analog mineral surfaces exposed to ultraviolet radiation under a simulated martian atmosphere. These oxygen radicals can explain the reactive nature of the soil and the apparent absence of organic material at the martian surface.

long duration↗

NASA NTRS2000

Evidence that the reactivity of the martian soil is due to superoxide ions

The Viking Landers were unable to detect evidence of Life on Mars but, instead, found a chemically reactive soil capable of decomposing organic molecules.

Oxide↗

DOE OSTI2024

LLNL FY24 Aging and Lifetimes Exit Criteria: Milestone 9134, GC#2, EC#2

Surface chemistry of uranium from gases in the ambient atmosphere of the application environment presents significant challenges due to the high degree of reactivity of the substrate and the ubiquity of these gases in experimental setups. Relatively little is known about the chemical mechanism and reaction rates for the catalytic dissociation of atmospheric gases on solid plutonium or uranium as well as the degradation process to form the metal hydride. Experimental studies and age-aware modeling efforts would greatly benefit from detailed atomistic knowledge of the chemical reactivity in these materials.

36 MATERIALS SCIENCE↗

NASA NTRS2005

Correlations of (Delta)O-17 with Chemical Characteristics Among Chondrite Groups

Demonstration of mass-independent O isotopic variations in solar system materials was a seminal discovery of meteoritics. These variations were thought to reflect incomplete mixing of O from different nucleosynthesis sources. Since then, two non-nucleosynthetic causes have been suggested: (1) differential photodissociation of distinct isotopomers of CO, enriching nebular gas in chemically reactive heavy O, and (2) gas-phase molecular reactions producing mass-independent O isotopic exchange. Nebular processes caused chemical fractionations that are observed in chondrite bulk compositions. If nebular processes also produced mass-independent O isotopic variations, then these may correlate with chondrite bulk chemistry.

Mittlefehldt, D. W.↗

DOE OSTI2023

Non-equilibrium low-temperature plasma-assisted combustion of iso-octane: Perturbing pyrolysis and oxidation kinetics

Here, in this study, a plasma-coupled flow reactor facility is used to examine the effects of non-equilibrium low-temperature plasmas on perturbing the pyrolysis and oxidation kinetics of iso-octane. Experiments were performed in highly dilute reactive mixtures of nitrogen, at near isothermal conditions for temperatures ranging from 523 K to 1203 K. Experiments cumulatively demonstrated enhanced chemical reactivity with the plasma for temperatures below 900 K, and a lowering of the hot-ignition temperature. Detailed kinetic insight was derived from a 0D plasma-coupled kinetic model, utilizing a constructed mechanism that combined both plasma-specific chemistry and the neutral combustion chemistry. For pyrolysis conditions, the model displayed relatively good agreement with fuel consumption and the formation of most intermediates compared to the experimental data, demonstrating the model is able to accurately predict primary radical formation from the plasma directly interacting with the fuel. Enhanced reactivity was attributed to collisional quenching of excited-states of N 2 with fuel, which led to efficient fuel fragmentation and enhancement of the H-radical flux. For oxidation conditions, the model displayed satisfactory agreement with the experiments. Model predictions were able to accurately predict fuel consumption and most intermediate speciation data for T > 800 K, but most discrepancies were towards T < 800 K in particular with oxygenated intermediates. In the presence of oxygen, plasma effects were predominantly spent on efficient enhancement of O- and H-radical fluxes, leading to further fuel fragmentation and initiation of both the OH- and HO 2 -radical pools. Subsequent reactivity of iso-octane was then dictated by the response of the temperature-dependent neutral chemistry. At low-temperatures (T = 643 K), enhanced fuel radicals and O 2 -additon chemistry lead to the formation of oxygenated species, while at intermediate temperatures (T = 843 K) net decrease in OH-radical reactivity led to an increase in hydrocarbon speciation. Near the self-ignition threshold (T = 1163 K), radicals generated by high-temperature branching reactions dominate the oxidation process and effectively ignition. This study ultimately demonstrated that the enhancement of radicals afforded by the plasma causes a deviation in known understanding of iso-octane kinetics in some regards and warrants future studies to reconcile these discrepancies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

NASA NTRS2022

Separating Propulsive Mass and Energy for Space Applications

Initially and traditionally, space access and in-space propulsion utilized combustion and expulsion of chemical “fuels” carried on board, with performance governed by the rocket equation. These chemicals produced energy, and after combustion, constituted the propulsive mass/momentum. The best such chemicals in terms of Isp that are deemed safe engineering/mission wise are hydrogen and oxygen, producing some 450 seconds of Isp. There are more reactive chemicals, such as fluorine, which have higher Isp, but also have serious safety issues. Propulsion in atmospheres can ingest atmospheric constituents (aka “airbreathing propulsion”) which provide additional propulsive mass when heated and a component of the combustion/energy generation process. This utilization of non-stored/carried propulsive mass provides partial separation of propulsive mass and energy and produces higher Isp. The other approach to separating propulsive mass and energy is to, either on board or added from offboard, supply additional energy, such as from nuclear or solar sources. This is the approach for fission nuclear thermal and electric propulsion, which can provide an Isp in excess of 800 seconds of Isp. Other processes or in addition to thermal expansion, such as electro-magnetics, can be employed to increase exit velocity and Isp. Separating propulsive mass and energy for space faring is commonly referred to as a means to circumvent the rocket equation and is capable of producing major benefits for the development of commercial deep space and space faring in general including affordable fast transits to mitigate the human health impacts of galactic cosmic radiation (GCR) and microG. The key to higher than chemical Isp, beyond H2-O2, and beyond the radiated energy and systems limitations of solar for space faring, is a light weight, high energy density source, either on board or via utilization of energy beaming to the vehicle. Traditional energy sources include chemical, heat, electrics, mechanical, photons, and nuclear. Propulsive mass can be carried on board, sourced beyond the surface of Earth via in-situ resource utilization (ISRU), and includes harvesting from atmospheres. High Isp via electromagnetic related propulsive mass acceleration requires sufficient ionization and conductivity. The major metrics for space propulsion are costs, safety, Isp, weight, and thrust level, the latter dependent upon mission requirements. High thrust for human missions is needed to reduce time exposed to radiation and microG and high thrust is required for space access. Costs of space access are reducing via reusability, printing manufacture, and robotization of manufacturing and operation. Chemical rockets provide high thrust from the expansion of the heated mass constituents at high mass flow. The other high thrust propulsion approach is magnetohydrodynamics (MHD), which, in addition to high thrust, has a high Isp of over 2,000 seconds of Isp. The VASIMIR engine offers some 5,000 seconds of Isp at high thrust [ref. 3]. Electric propulsion cycles are capable of Isp much higher than that but at low thrust levels using available energy sources. With cost as a major metric, reusable rockets and improved manufacturing and operations are rapidly greatly lowering the costs of space access, which could provide/supply in space fuel depots and affordable chemical propulsion for the desired human fast transits (e.g., some 200-day round trips to Mars). The other option for fast transits is VASIMIR, given a nuclear on-board energy source that has the requisite many megawatts of power and an alpha, kgs of weight/kW of energy produced, on the order of one (i.e., a light weight, high energy density energy source). The purpose of this report is to examine the options beyond traditional rocket engines, where propulsive mass and energy are combined, specifically the separation of propulsive mass and energy. This report considers the spectrum of advanced energetics, sources of propulsive mass, conductivity enhancement approaches, energy beaming possibilities, and candidate propulsion cycles. Suggestions are made for various combinatorial, system level, beyond traditional combustion rocket, space propulsion approaches for human deep space missions given the changing conditions of increased knowledge of deep space resources for ISRU, revolutionary energetics, and technology advancements writ large.

Dennis M. Bushnell↗