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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Mechanism of the Accelerated Water Formation Reaction under Interfacial Confinement

Subnanoscale spaces at the interface between weakly coupled thin films and their metal supports offer exciting opportunities for studying chemical reactions under confinement. Here, we investigated the kinetics of water formation (from hydrogen and chemisorbed oxygen) in the confined space at the interface between bilayer (BL) silica and a Ru(0001) support, compared to the reaction on the bare Ru(0001) surface. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments were carried out at different temperatures at elevated pressures of H 2 to follow the reaction kinetics. The apparent activation energy at the BL-silica/Ru(0001) interface was found to be 0.38 eV lower than that on bare Ru(0001), consistent with a recent report by Prieto et al. (Angew. Chem., Int. Ed.2018, 57(28), 8749–8753) carried out at lower H 2 pressures using low-energy electron microscopy. Density functional theory calculations revealed that the rate-limiting step in the direct hydrogenation pathway on the Ru(0001) surface is the first hydrogen addition step (*H + *O ↔ *OH). The confinement at the BL-silica/Ru(0001) interface only marginally affects the energy barrier of the first hydrogen addition. Instead, it activates an alternative disproportionation reaction pathway (*H 2 O + *O ↔ 2*OH). On the bare Ru(0001) surface, the disproportionation pathway can only occur at cryogenic temperatures or under high water vapor pressures. However, the presence of the BL-silica increases the desorption barrier for water molecules at the interface. The increased residence time allows trapped water molecules to react with chemisorbed oxygen to produce two *OH per H 2 O with an activation energy 0.25 eV lower than that of the first hydrogen addition step. Finally, this work reveals the origin of the observed accelerated water formation reaction at the BL-silica/Ru(0001) interface in the low-temperature regime (T < 350 K) and points to a route to engineer chemical reaction pathways by leveraging subnanoscale confined spaces at metal–oxide interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Performance and Durability of Hybrid Fuel Cell Systems for Class-8 Long Haul Trucks

Hybrid fuel cell-battery configurations are investigated that overcome thermal management issues in fuel cell powertrains for heavy-duty Class 8 trucks. The battery is sized so that it has sufficient capacity to provide supplemental power and energy on a hill climb transient at end-of-life. A dynamic load sharing strategy is developed to distribute the power demand between the fuel cell system (FCS) and the energy storage system in a manner that optimizes their lifetimes. The FCS end-of-life is identified as the terminal point beyond which the stack cannot generate the rated power with target power density at 0.7 V and 40 °C ambient temperature. Reaching the target lifetime with a-Pt/C cathode catalyst in one hybrid configuration requires voltage clipping to 813 mV, idle power limited to 50 kW, catalyst overloading to 0.45 mg cm -2 total Pt in anode and cathode, and 44% active membrane area oversizing. The stack and FCS drive cycle efficiencies decrease by 4.2% and 5.4%, respectively, during the electrode lifetime. Further, the FCS performance, durability and cost are compared with the targets of 68% peak efficiency, 0.30 mg cm -2 total Pt loading, 2.5 kW/g PGM Pt group metal (PGM) loading, 750 mW cm -2 power density, 25,000-h lifetime and $80/kW cost.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS2011

Lunar Solar Origins Exploration (LunaSOX)

The Moon offers a unique vantage point from which to investigate the Sun and its interaction via the solar wind magnetic fields, plasma, and energetic particles with the geospace system including the Moon itself. The lunar surface and exosphere provide in part a record of solar coronal plasma material input and resultant space weathering over billions of years. The structure and dynamics of solar wind interactions with the Moon provide an accessible near-Earth laboratory environment for study of general solar wind interactions with the vast multitude of airless asteroidal bodies of the inner solar system. Spacecraft in lunar orbit have the often simultaneous opportunity, except when in the Earth's magnetosphere, to make in-situ compositional measurements of the solar wind plasma and to carry out remote observations from the Moon of the solar corona, potentially enabled by lunar limb occultation of the solar disk. The LunaSOX project at NASA Goddard Space Flight Center is addressing these heliophysical science objectives from and of the Moon with support from NASA's Lunar Advanced Science and Exploration Research (LASER) program: (1) specify history of solar wind parameters at and sunward of the Moon through enhanced access (http://lunasox.gsfc.nasa.gov/) to legacy and operational mission data products from the Apollo era to the present, (2) model field and plasma interactions with the lunar surface, exosphere, and wake, as constrained by the available data, through hybrid kinetic code simulations, and (3) advance mission concepts for heliophysics from and of the Moon.

Cooper, John F.↗
DOE OSTI2024

Simulations of classical three-body thermalization in one dimension

One-dimensional systems, such as nanowires or electrons moving along strong magnetic field lines, have peculiar thermalization physics. The binary collision of pointlike particles, typically the dominant process for reaching thermal equilibrium in higher-dimensional systems, cannot thermalize a 1D system. We study how dilute classical 1D gases thermalize through three-body collisions. We consider a system of identical classical point particles with pairwise repulsive inverse power-law potential V ij ∝ 1/|x i –x j | n or the pairwise Lennard-Jones potential. Using Monte Carlo methods, we compute a collision kernel and use it in the Boltzmann equation to evolve a perturbed thermal state with temperature T toward equilibrium. We explain the shape of the kernel and its dependence on the system parameters. Additionally, we implement molecular dynamics simulations of a many-body gas and show agreement with the Boltzmann evolution in the low-density limit. For the inverse power-law potential, the rate of thermalization is proportional to ρ 2 ⁢T$\frac{1}{2}$ – $\frac{1}{n}$, where ρ is the number density. Furthermore, the corresponding proportionality constant decreases with increasing n.

1-dimensional systems↗
DOE OSTI2023

n-Propylbenzene Droplet Combustion: Experiments and Numerical Modeling

n-Propylbenzene (PB, C9H12, 432K boiling point) is important as a constituent in surrogates for some transportation fuels but little is understood about its droplet burning characteristics. We present an experimental and numerical study of a fuel droplet burning under conditions where the sole means of gas transport is fuel evaporation at the droplet surface thereby creating a one-dimensional gas transport that is amenable to detailed numerical modeling. The one-dimensional gas transport that results is amenable to detailed numerical modeling. Initial droplet diameters (Do) ranged from 0.3 mm to about 5 mm to better understand the mechanisms that control burning over such a wide range of Do. For Do < 1 mm droplets were burned while anchored to 14 m SiC fibers within a sealed container in free-fall during which time the droplets were ignited by spark discharge and the burning process recorded by video cameras. Larger and free-floating droplets were studied in the spaced-based platform of the orbiting International Space Station for Do > 1.0 mm which provided unlimited times for experimental observation. Measurements of droplet, flame and soot shell diameters were made and are discussed in the presentation. The experimental results showed formation of optically thick soot clouds developing during burning that required a robust image analysis algorithm to enable measurement of droplet diameter. The measured droplet diameters were well predicted by a numerical model that included soot formation, a PB kinetic mechanism comprising 576 species and 27369 reactions, unsteady gas and liquid transport, variable properties and radiative transport. Flame diameters showed more variability compared to the simulations, depending on how the flame was defined (peak gas temperature and OH concentration). Droplets burned slower as Do was increased and the PB sooting propensity increased with Do. Flame extinction was observed for Do > 3.3 mm indicating a strong effect of radiation as Do was increased compared to the smaller droplet diameters examined where extinction was not experimentally observed. For the largest droplets examined the possibility that the observed extinction is indicative of a transition to cool flame burning is still under investigation.

Guo, Songtao↗
DOE OSTI2021

(Invited) Understanding Multi-Component Transport and Reaction Phenomena in Bipolar Membranes Used for Electrosynthesis

Bipolar membranes (BPMs), which have long seen usage in electrodialysis reactors for the generation of acid and base, have recently demonstrated potential to become critical components in electrochemical synthesis devices. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM junction as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-devices for electrosynthesis applications. Prior work has modeled ion transport in bipolar membranes in neutral salt solutions for electrodialysis. However, no model exists for the BPM under the harsh applied pH gradients that would be present in electrosynthesis, and there is significant need to explore the effects of the internal hydration on the lifetime and performance of BPMs in such environments. Additionally, a mechanistic understanding of water dissociation catalysis will be required to develop interfacial catalysts that enable the high current density operation required for scalable electrosynthesis of fuels. In this talk, we discuss modeling methodologies and physics inherent in BPMs and present our recent model of ion transport and water dissociation catalysis in BPMs across the pH scale. Specifically, we simulate multi-ion transport for a BPM with various electrolyte combinations on each side of the membrane, demonstrating the significance of co- and counter-ion crossover in BPMs operating under harsh pH gradients. We then investigate effects caused by hydration gradients that occur due to internal ion-exchange and examine potential methods for improving performance and mitigating crossover. Finally, we examine the impact of the interfacial water dissociation catalyst and perform sensitivity analysis on the key properties (catalyst point of zero charge and pKa) that dictate catalyst performance. These results provide information that is critical to developing a comprehensive understanding of multi-component phenomena in BPMs and to informing the design and implementation of BPMs in next-generation devices for the numerous electrosynthesis chemistries that benefit from operation under an applied pH gradient.

Bui, Justin C↗
DOE OSTI2022

Reactions of hydrazine with the amidogen radical and atomic hydrogen

The rate coefficient k 1 for NH 2 + N 2 H 4 was measured to be (5.4 ± 0.4) × 10 –14 cm 3 molecule –1 s –1 at 296 K. NH 2 was generated by pulsed laser photolysis of NH 3 at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N 2 H 4 in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k 1 = 6.3 × 10 –23 T 3.44 exp(+289 K/T) cm 3 molecule –1 s –1 . The minor channel for H + N 2 H 4 forming NH 2 + NH 3 was characterized computationally as well, to yield 5.0 × 10 –19 T 2.07 exp(-4032 K/T) cm 3 molecule –1 s –1 . Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Turbulent Plane Wakes Subjected to Successive Strains

Six direct numerical simulations of turbulent time-evolving strained plane wakes have been examined to investigate the response of a wake to successive irrotational plane strains of opposite sign. The orientation of the applied strain field has been selected so that the flow is the time-developing analogue of a spatially developing wake evolving in the presence of either a favourable or an adverse streamwise pressure gradient. The magnitude of the applied strain rate a is constant in time t until the total strain e(sup at) reaches about four. At this point, a new simulation is begun with the sign of the applied strain being reversed (the original simulation is continued as well). When the total strain is reduced back to its original value of one, yet another simulation is begun with the sign of the strain being reversed again back to its original sign. This process is done for both initially "favourable" and initially "adverse" strains, providing simulations for each of these strain types from three different initial conditions. The evolution of the wake mean velocity deficit and width is found to be very similar for all the adversely strained cases, with both measures rapidly achieving exponential growth at the rate associated with the cross-stream expansive strain e(sup at). In the "favourably" strained cases, the wake widths approach a constant and the velocity deficits ultimately decay rapidly as e(sup -2at). Although all three of these cases do exhibit the same asymptotic exponential behaviour, the time required to achieve this is longer for the cases that have been previously adversely strained (by at approx. equals 1). These simulations confirm the generality of the conclusions drawn in Rogers (2002) regarding the response of plane wakes to strain. The evolution of strained wakes is not consistent with the predictions of classical self-similar analysis; a more general equilibrium similarity solution is required to describe the results. At least for the cases considered here, the wake Reynolds number and the ratio of the turbulent kinetic energy to the square of the wake mean velocity deficit are determined nearly entirely by the total strain. For these measures the order in which the strains are applied does not matter and the changes brought about by the strain are nearly reversible. The wake mean velocity deficit and width, on the other hand, differ by about a factor of three when the total strain returns to one, depending on whether the wake was first "favourably" or "adversely" strained. The strain history is important for predicting the evolution of these quantities.

Rogers, Michael M.↗
DOE OSTI2024

Large-Eddy Simulation Study of Flow and Combustion Dynamics in a Full-Scale Hydrogen–Air Rotating Detonation Combustor-Stator Integrated System

In the present work, a first-of-its-kind three-dimensional (3D) large-eddy simulation (LES) study is conducted to numerically investigate the combustion dynamics as well as aero-thermal phenomena in a full-scale nonpremixed hydrogen–air rotating detonation engine (RDE) (with a diverging-shaped lower-end wall), when integrated with nozzle guide vanes (NGV) acting as the turbine stator. The wall-modeled LES framework incorporates hydrogen–air detailed chemical kinetics and adaptive mesh refinement (AMR). A comparative analysis is carried out for two operating conditions with different fuel/air mass flow rates but global equivalence ratio of unity, and considering RDE configurations without and with stator. The LES model is validated against available experimental data for the low mass flux condition with respect to detonation wave speed/height, wave dynamics, and axial static pressure distribution. Numerical results indicate significant deflagrative combustion occurring in the fill region near the inner wall due to formation of recirculation zones in the injection near-field driven by the backward facing step. The leading detonation wave is found to be trailed by an azimuthal reflected-shock combustion (ARSC) wave, consistent with experimental observations, which consumes unburned vitiated reactants that leak through the main detonation wave. The main detonation wave characteristics, such as detonation wave speed/height and combustion efficiency, do not change appreciably with the presence of NGV. A novel combustion diagnostic technique based on chemical explosive mode analysis (CEMA) is employed to quantify the fraction of heat release occurring in the detonative mode versus deflagrative mode for the simulated conditions. The exit flow is found to be nearly fully subsonic and supersonic for the low and high mass flux conditions, respectively. Further analysis of the exit flow profiles shows that the presence of NGV renders the flow more axial and significantly impacts the exit Mach number and total pressure, while the total temperature shows negligible change. In addition, the low mass flux operating point, despite exhibiting more deflagrative losses within the combustor, yields overall lower pressure drop from plenum to exhaust, which is mainly attributed to lower pressure drop across the injectors. Lastly, the rotating detonation engine-nozzle guide vanes (RDE-NGV) configuration exhibits higher total pressure loss compared to rotating detonation engine (RDE) without stator across both the mass flux conditions. In conclusion, this study extends the state-of-the-art in numerical modeling of pressure gain combustion (PGC) systems by demonstrating high-fidelity 3D reacting LES of full-scale RDE-NGV systems relevant to RDE-turbine integration for stationary power generation.

Combustion↗
DOE OSTI2021

Conformal maps of viscous electron flow in the Gurzhi crossover

Herein we investigate the impact of geometric constriction on the viscous flow of electron liquid through quantum point contacts. We provide analysis on the electric potential distribution given the setup of a slit configuration and use the method of conformal mapping to obtain analytical results. The potential profile can be tested and contrasted experimentally with the scanning tunneling potentiometry technique. We discuss intricate physics that underlies the Gurzhi effect, i.e., the enhancement of conductivity in the viscous flow, and compare results for different boundary conditions. In addition, we calculate the temperature dependence of the momentum relaxation time as a result of impurity assisted quasiballistic interference effects and discuss various correlational corrections that lead to the violation of Matthiessen's rule in the hydrodynamic regime. We caution that spatially inhomogeneous profiles of current in the Gurzhi crossover between Ohmic and Stokes flows might also appear in the nonhydrodynamic limit where nonlocality plays an important role. This conclusion is corroborated by calculation of dispersive conductivity in the weakly impure limit.

2-dimensional systems↗
DOE OSTI2026

Precision Kinematic Sunyaev--Zel'dovich Measurements Across Halo Mass and Redshift with DESI DR2 and ACT DR6: Part II. Bright Galaxy Survey and Emission-Line Galaxies

We present the first high-significance spectroscopic stacked kinetic Sunyaev-Zel'dovich (kSZ) measurements of circumgalactic gas profiles for both Bright Galaxy Survey (BGS) and Emission Line Galaxy (ELG) tracers, combining DESI Data Release 2 with ACT Data Release 6. Using reconstructed line-of-sight velocities from the DESI galaxies and high-resolution ACT temperature maps, we detect the kSZ signal at high significance, reaching signal-to-noise ratios of up to $\sim$9 for BGS and $\sim$7.5 for ELGs in optimal stellar-mass selections. Together with the LRG measurements presented in Paper I, these constitute the most significant kSZ detections from any spectroscopic survey to date. We perform the analysis in both real and harmonic space, obtaining consistent results. By splitting both tracers into stellar-mass bins, we study the scaling of the kSZ amplitude with galaxy properties. Combining the kSZ measurements with ACT Data Release 6 (DR6) CMB lensing maps enables a joint calibration of the galaxy-halo connection and the gas fractions of host halos. For the BGS galaxies, we observe low gas fractions around the virial radius relative to standard expectations, likely attributable to active galactic nuclei (AGN) activity. We find some evidence for higher-mass halos retaining a larger fraction of their baryons, consistent with more efficient feedback in lower-mass systems. For the ELG sample, dominated by blue, star-forming galaxies, we provide the first detection of the gas distribution in ELG host halos. The ELGs appear to exhibit relatively high gas fractions, which points to the possibility of weaker feedback (due to e.g. low AGN and supernova feedback activity) at their mass scale. Finally, we present generalized Navarro-Frenk-White (GNFW) fits to the harmonic-space measurements, providing a compact parametrization of gas profiles for forward modeling in large-scale structure analyses.

Hadzhiyska, B. [Cambridge U.; Cambridge U., Inst. ↗
NASA NTRS1995

Modeling and simulation of a turbulent far wake

Work continued on two projects which had been started during previous years. Both projects involve calculations of the subsonic, turbulent far wake of a two-dimensional object at a Reynolds number of 1000 (based on wake momentum thickness). This flow was used as a test case for direct comparison of various turbulence models and a direct numerical simulations (DNS) of this flow were undertaken. In the turbulence model comparison studies, for any particular model tested, a unique self-similar solution was obtained far enough downstream, regardless of inlet conditions. Furthermore, different turbulence models led to different far-wake equilibrium solutions. No turbulence model could correctly predict all features of the turbulent far wake. For example, the spreading rate and turbulent shear stresses were underpredicted by all the standard models (both two-equation and full Reynolds stress models). In cases where a more correct spreading rate was achieved, it was at the expense of the turbulent kinetic energy, which was overpredicted. In general, the Algebraic Dissipation Rate Model of Gatski and Speziale, 1992, when added to any of the standard models, improved the results dramatically. Also, full Reynolds stress closure models did a much better job at predicting the shapes of both the mean and turbulence profiles, but the spreading rate was not significantly improved over that predicted by the simpler two-equation models. There are two main conclusions from these studies: First, in a comparison such as this, it is not enough to compare just one parameter, like the spreading rate. A good prediction for one parameter does not necessarily imply good predictions for all parameters in a flow. Second, since no turbulence model could correctly predict the turbulent far wake, much of the important physics of turbulent free shear flows is apparently lost by the assumptions inherent in today's methods of turbulence modeling; turbulence models must be improved. Direct simulations of this flow were begun last year in order to provide a data base through which some of the deficiencies of the existing turbulence models could be identified. Quantities such as the pressure-strain correlation, turbulent diffusion, and the dissipation rate tensor can be easily calculated from the DNS results, whereas these quantities are nearly impossible to measure experimentally. Improvements to existing turbulence models (and development of new models) require knowledge about flow quantities such as these. During this summer, diagnostics codes were written which will calculate the parameters mentioned above, along with other single-point and multi-point statistics. The DNS calculations are still in progress at the time of this writing. When these calculations are complete, the diagnostics codes will be applied so that the results can aid turbulence modelers. In addition, the results will show whether or not there exists a universal equilibrium turbulent far wake, independent of initial conditions.

Cimbala, John M.↗
NASA NTRS2004

Application of Simulated Annealing and Related Algorithms to TWTA Design

Simulated Annealing (SA) is a stochastic optimization algorithm used to search for global minima in complex design surfaces where exhaustive searches are not computationally feasible. The algorithm is derived by simulating the annealing process, whereby a solid is heated to a liquid state and then cooled slowly to reach thermodynamic equilibrium at each temperature. The idea is that atoms in the solid continually bond and re-bond at various quantum energy levels, and with sufficient cooling time they will rearrange at the minimum energy state to form a perfect crystal. The distribution of energy levels is given by the Boltzmann distribution: as temperature drops, the probability of the presence of high-energy bonds decreases. In searching for an optimal design, local minima and discontinuities are often present in a design surface. SA presents a distinct advantage over other optimization algorithms in its ability to escape from these local minima. Just as high-energy atomic configurations are visited in the actual annealing process in order to eventually reach the minimum energy state, in SA highly non-optimal configurations are visited in order to find otherwise inaccessible global minima. The SA algorithm produces a Markov chain of points in the design space at each temperature, with a monotonically decreasing temperature. A random point is started upon, and the objective function is evaluated at that point. A stochastic perturbation is then made to the parameters of the point to arrive at a proposed new point in the design space, at which the objection function is evaluated as well. If the change in objective function values (Delta)E is negative, the proposed new point is accepted. If (Delta)E is positive, the proposed new point is accepted according to the Metropolis criterion: rho((Delta)f) = exp((-Delta)E/T), where T is the temperature for the current Markov chain. The process then repeats for the remainder of the Markov chain, after which the temperature is decremented and the process repeats. Eventually (and hopefully), a near-globally optimal solution is attained as T approaches zero. Several exciting variants of SA have recently emerged, including Discrete-State Simulated Annealing (DSSA) and Simulated Tempering (ST). The DSSA algorithm takes the thermodynamic analogy one step further by categorizing objective function evaluations into discrete states. In doing so, many of the case-specific problems associated with fine-tuning the SA algorithm can be avoided; for example, theoretical approximations for the initial and final temperature can be derived independently of the case. In this manner, DSSA provides a scheme that is more robust with respect to widely differing design surfaces. ST differs from SA in that the temperature T becomes an additional random variable in the optimization. The system is also kept in equilibrium as the temperature changes, as opposed to the system being driven out of equilibrium as temperature changes in SA. ST is designed to overcome obstacles in design surfaces where numerous local minima are separated by high barriers. These algorithms are incorporated into the optimal design of the traveling-wave tube amplifier (TWTA). The area under scrutiny is the collector, in which it would be ideal to use negative potential to decelerate the spent electron beam to zero kinetic energy just as it reaches the collector surface. In reality this is not plausible due to a number of physical limitations, including repulsion and differing levels of kinetic energy among individual electrons. Instead, the collector is designed with multiple stages depressed below ground potential. The design of this multiple-stage collector is the optimization problem of interest. One remaining problem in SA and DSSA is the difficulty in determining when equilibrium has been reached so that the current Markov chain can be terminated. It has been suggested in recent literature that simulating the thermodynamic properties opecific heat, entropy, and internal energy from the Boltzmann distribution can provide good indicators of having reached equilibrium at a certain temperature. These properties are tested for their efficacy and implemented in SA and DSSA code with respect to TWTA collector optimization.

Radke, Eric M.↗
NASA NTRS2001

Carbon Dioxide Clouds at High Altitude in the Tropics and in an Early Dense Martian Atmosphere

We use a time dependent, microphysical cloud model to study the formation of carbon dioxide clouds in the Martian atmosphere. Laboratory studies by Glandor et al. show that high critical supersaturations are required for cloud particle nucleation and that surface kinetic growth is not limited. These conditions, which are similar to those for cirrus clouds on Earth, lead to the formation of carbon dioxide ice particles with radii greater than 500 micrometers and concentrations of less than 0.1 cm(exp -3) for typical atmospheric conditions. Within the current Martian atmosphere, CO2 cloud formation is possible at the poles during winter and at high altitudes in the tropics during periods of increased atmospheric dust loading. In both cases, temperature perturbations of several degrees below the CO2 saturation temperature are required to nucleate new cloud particles suggesting that dynamical processes are the most common initiators of carbon dioxide clouds rather than diabatic cooling. The microphysical cloud model, coupled to a two-stream radiative transfer model, is used to reexamine the impact of CO2 clouds on the surface temperature within a dense CO2 atmosphere. The formation of carbon dioxide clouds leads to a warmer surface than what would be expected for clear sky conditions. The amount of warming is sensitive to the presence of dust and water vapor in the atmosphere, both of which act to dampen cloud effects. The radiative warming associated with cloud formation, as well as latent heating, work to dissipate the clouds when present. Thus, clouds never last for periods much longer than several days, limiting their overall effectiveness for warming the surface. The time average cloud optical depth is approximately unity leading to a 5-10 K warming, depending on the surface pressure. However, the surface temperature does not rise about the freezing point of liquid water even for pressures as high as 5 bars, at a solar luminosity of 75% the current value.

Colaprete, Anthony↗
NASA NTRS1992

Reactant conversion in homogeneous turbulence: Mathematical modeling, computational validations and practical applications

Closed form analytical expressions are obtained for predicting the limited rate of reactant conversion in a binary reaction of the type F + rO yields (1 + r) Product in unpremixed homogeneous turbulence. These relations are obtained by means of a single point Probability Density Function (PDF) method based on the Amplitude Mapping Closure. It is demonstrated that with this model, the maximum rate of the reactants' decay can be conveniently expressed in terms of definite integrals of the Parabolic Cylinder Functions. For the cases with complete initial segregation, it is shown that the results agree very closely with those predicted by employing a Beta density of the first kind for an appropriately defined Shvab-Zeldovich scalar variable. With this assumption, the final results can also be expressed in terms of closed form analytical expressions which are based on the Incomplete Beta Functions. With both models, the dependence of the results on the stoichiometric coefficient and the equivalence ratio can be expressed in an explicit manner. For a stoichiometric mixture, the analytical results simplify significantly. In the mapping closure, these results are expressed in terms of simple trigonometric functions. For the Beta density model, they are in the form of Gamma Functions. In all the cases considered, the results are shown to agree well with data generated by Direct Numerical Simulations (DNS). Due to the simplicity of these expressions and because of nice mathematical features of the Parabolic Cylinder and the Incomplete Beta Functions, these models are recommended for estimating the limiting rate of reactant conversion in homogeneous reacting flows. These results also provide useful insights in assessing the extent of validity of turbulence closures in the modeling of unpremixed reacting flows. Some discussions are provided on the extension of the model for treating more complicated reacting systems including realistic kinetics schemes and multi-scalar mixing with finite rate chemical reactions in more complex configurations.

Madnia, C. K.↗
DOE OSTI2022

On the use of vibronic coherence to identify reaction coordinates for ultrafast excited-state dynamics of transition metal-based chromophores

In this study, the question of whether one can use information from quantum coherence as a means of identifying vibrational degrees of freedom that are active along an excited-state reaction coordinate is discussed. Specifically, we are exploring the notion of whether quantum oscillations observed in single-wavelength kinetics data exhibiting coherence dephasing times that are intermediate between that expected for either pure electronic or pure vibrational dephasing are vibronic in nature and therefore may be coupled to electronic state-to-state evolution. In the case of a previously published Fe(ιι) polypyridyl complex, coherences observed subsequent to 1 A 1 → 1 MLCT excitation were linked to large-amplitude motion of a portion of the ligand framework; dephasing times on the order of 200–300 fs suggested that these degrees of freedom could be associated with ultrafast (~100 fs) conversion from the initially formed MLCT excited state to lower-energy, metal-centered ligand-field excited state(s) of the compound. Incorporation of an electronically benign but sterically restrictive Cu(ι) ion into the superstructure designed to interfere with this motion yielded a compound exhibiting a ~25-fold increase in the compound’s MLCT lifetime, a result that was interpreted as confirmation of the initial hypothesis. However, new data acquired on a different chemical system – Cr(acac') 3 (where acac' represents various derivatives of acetylacetonate) – yielded results that call into question this same hypothesis. Coherences observed subsequent to 4 A 2 → 4 T 2 ligand-field excitation on a series of molecules implicated similar vibrational degrees of freedom across the series, but exhibited dephasing times ranging from 340 fs to 2.5 ps without any clear correlation to the dynamics of excited-state evolution in the system. Taken together, the results obtained on both of these chemical platforms suggest that while identification of coherences can indeed point to degrees of freedom that should be considered as candidate modes for defining reaction trajectories, our understanding of the factors that determine the interplay across coherences, dephasing times, and electronic and geometric structure is insufficient at the present time to view this parameter as a robust metric for differentiating active versus spectator modes for ultrafast dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Cloud droplet diffusional growth in homogeneous isotropic turbulence: bin microphysics versus Lagrangian super-droplet simulations

The increase in the spectral width of an initially monodisperse population of cloud droplets in homogeneous isotropic turbulence is investigated by applying a finite-difference fluid flow model combined with either Eulerian bin microphysics or a Lagrangian particle-based scheme. The turbulence is forced applying a variant of the so-called linear forcing method that maintains the mean turbulent kinetic energy (TKE) and the TKE partitioning between velocity components. The latter is important for maintaining the quasi-steady forcing of the supersaturation fluctuations that drive the increase in the spectral width. We apply a large computational domain (64 3 m 3 ), one of the domains considered in Thomas et al. (2020). The simulations apply 1 m grid length and are in the spirit of the implicit large eddy simulation (ILES), that is, with small-scale dissipation provided by the model numerics. This is in contrast to the scaled-up direct numerical simulation (DNS) applied in Thomas et al. (2020). Two TKE intensities and three different droplet concentrations are considered. Analytic solutions derived in Sardina et al. (2015), valid for the case when the turbulence integral timescale is much larger than the droplet phase relaxation timescale, are used to guide the comparison between the two microphysics simulation techniques. The Lagrangian approach reproduces the scalings relatively well. Representing the spectral width increase in time is more challenging for the bin microphysics because appropriately high resolution in the bin space is needed. The bin width of 0.5 µm is only sufficient for the lowest droplet concentration (26 cm -3 ). For the highest droplet concentration (650 cm -3 ), an order of magnitude smaller bin size is barely sufficient. The scalings are not expected to be valid for the lowest droplet concentration and the high-TKE case, and the two microphysics schemes represent similar departures. Finally, because the fluid flow is the same for all simulations featuring either low or high TKE, one can compare point-by-point simulation results. Such a comparison shows very close temperature and water vapor point-by-point values across the computational domain and larger differences between simulated mean droplet radii and spectral width. The latter are explained by fundamental differences in the two simulation methodologies, numerical diffusion in the Eulerian bin approach and a relatively small number of Lagrangian particles that are used in the particle-based microphysics.

54 ENVIRONMENTAL SCIENCES↗