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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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Reorganization Energies for Interfacial Proton-Coupled Electron Transfer to a Water Oxidation Catalyst
The reorganization energy (λ) for interfacial electron transfer (ET) and proton-coupled electron transfer (PCET) from a conductive metal oxide (In 2 O 3 :Sn, ITO) to a surface-bound water oxidation catalyst were extracted from kinetic data measured as a function of the thermodynamic driving force. Visible light excitation resulted in rapid excited-state injection (k inj > 10 8 s -1 ) to the ITO, which photo-initiated the two interfacial reactions of interest. The rate constants for both reactions increased with the driving force, −ΔG°, to a saturating limit, k max , with rate constants consistently larger for ET than for PCET. Marcus-Gerischer analysis of the kinetic data provided the reorganization energy for interfacial PCET (0.90 ± 0.02 eV) and ET (0.40 ± 0.02 eV), respectively. The magnitude of k max for PCET was found to decrease with pH, behavior that was absent for ET. Both the decrease in k max and the larger reorganization energy for an unwanted competing PCET reaction from the ITO to the oxidized catalyst showcases a significant kinetic advantage for driving solar water oxidation at high pH. Computational analysis revealed a larger inner-sphere reorganization energy contribution for PCET than for ET arising from a more significant change in the Ru–O bond length for PCET. Extending Marcus-Gerischer theory to PCET by including the excited electron-proton vibronic states and the proton donor-acceptor motion provided an apparent reorganization energy of 1.01 eV. Furthermore, this study demonstrates that the Marcus-Gerischer theory initially developed for ET can be reliably extended to PCET for quantifying and interpreting reorganization energies observed experimentally.
Isolating and quantifying cross-beam energy transfer in direct-drive implosions on OMEGA and the National Ignition Facility
The angularly resolved mass ablation rates and ablation-front trajectories for Si-coated CH targets were measured in direct-drive inertial confinement fusion experiments to quantify cross-beam energy transfer (CBET) while constraining the hydrodynamic coupling. A polar-direct-drive laser configuration, where the equatorial laser beams were dropped and the polar beams were repointed from a symmetric direct-drive configuration, was used to limit CBET at the pole while allowing it to persist at the equator. The combination of low- and high-CBET conditions observed in the same implosion allowed for the effects of CBET on the ablation rate and ablation pressure to be determined. Hydrodynamic simulations performed without CBET agreed with the measured ablation rate and ablation-front trajectory at the pole of the target, confirming that the CBET effects on the pole are small. The simulated mass ablation rates and ablation-front trajectories were in excellent agreement with the measurements at all angles when a CBET model based on Randall's equations [C. J. Randall et al., Phys. Fluids 24, 1474 (1981)] was included into the simulations with a multiplier on the CBET gain factor. These measurements were performed on OMEGA and at the National Ignition Facility to access a wide range of plasma conditions, laser intensities, and laser beam geometries. The presence of the CBET gain multiplier required to match the data in all of the configurations tested suggests that additional physics effects, such as intensity variations caused by diffraction, polarization effects, or shortcomings of extending the 1-D Randall model to 3-D, should be explored to explain the differences in observed and predicted drive.
Chlorophyll–carotenoid excitation energy transfer and charge transfer in Nannochloropsis oceanica for the regulation of photosynthesis
Nonphotochemical quenching (NPQ) is a proxy for photoprotective thermal dissipation processes that regulate photosynthetic light harvesting. The identification of NPQ mechanisms and their molecular or physiological triggering factors under in vivo conditions is a matter of controversy. In this work, to view chlorophyll (Chl)–zeaxanthin (Zea) excitation energy transfer (EET) and charge transfer (CT) as possible NPQ mechanisms, we performed transient absorption (TA) spectroscopy on live cells of the microalga Nannochloropsis oceanica . We gained evidence for the operation of both EET and CT quenching by observing spectral features associated with the Zea S 1 and Zea •+ excited-state absorption (ESA) signals, respectively, after Chl excitation. Knockout mutants for genes encoding either violaxanthin de-epoxidase or LHCX1 proteins exhibited strongly inhibited NPQ capabilities and lacked detectable Zea S 1 and Zea •+ ESA signals in vivo, which strongly suggests that the accumulation of Zea and active LHCX1 is essential for both EET and CT quenching in N. oceanica .
Convective Heat Transfer Coefficients of Automatic Transmission Fluid Jets with Implications for Electric Machine Thermal Management: Preprint
Thermal management for electric machines (motors/ generators) is important as the automotive industry continues to transition to more electrically dominant vehicle propulsion systems. Cooling of the electric machine(s) in some electric vehicle traction drive applications is accomplished by impinging automatic transmission fluid (ATF) jets onto the machine's copper windings. In this study, we provide the results of experiments characterizing the thermal performance of ATF jets on surfaces representative of windings, using Ford's Mercon LV ATF. Experiments were carried out at various ATF temperatures and jet velocities to quantify the influence of these parameters on heat transfer coefficients. Fluid temperatures were varied from 50 degrees C to 90 degrees C to encompass potential operating temperatures within an automotive transaxle environment. The jet nozzle velocities were varied from 0.5 to 10 m/s. The experimental ATF heat transfer coefficient results provided in this report are a useful resource for understanding factors that influence the performance of ATF-based cooling systems for electric machines.
Heat and mass-transfer characteristics of an axial-flow liquid-core nuclear rocket employing radiation heat transfer
Heat and mass transfer characteristics of axial- flow liquid-core nuclear rocket engine employing radiation heat transfer
Demonstrating GPU code portability and scalability for radiative heat transfer computations
High performance computing frameworks utilizing CPUs, Nvidia GPUs, and/or Intel Xeon Phis necessitate portable and scalable solutions for application developers. Nvidia GPUs in particular present numerous portability challenges with a different programming model, additional memory hierarchies, and partitioned execution units among streaming multiprocessors. This work presents modifications to the Uintah asynchronous many-task runtime and the Kokkos portability library to enable one single codebase for complex multiphysics applications to run across different architectures. Scalability and performance results are shown on multiple architectures for a globally coupled radiation heat transfer simulation, ranging from a single node to 16,384 Titan compute nodes.
Prediction of the Thermal Runaway Limit and Optimal Operation of Heat Transfer-Limited, Fixed-Bed Reactor Systems
Here, we derive a new prediction for thermal runaway starting from the alpha model for fixed-bed reactor systems. This method accounts for thermal resistance internal to the reactor tube and the radial temperature gradients that result. To showcase our method, we compare its predictions to other common criteria for thermal runaway using o-xylene oxidation as the example chemistry. Even in systems where internal heat transfer is negligible, the empirical practical design criterion for thermal runaway is inaccurate. For cases where internal heat transfer is relevant, our runaway limit is more stringent than limits derived from simpler 1-D models. To augment our work, we optimize the product yield with the thermal runaway constraint using orthogonal collocation. Using the alpha model, the results illustrate that the thermal runaway limit can be accurately determined using either numerical or analytical methods.
110th Anniversary : Thermal Coupling via Heat Transfer: A Potential Route to Simple Distillation Configurations with Lower Heat Duty
Numerous configurations are available for the separation of a multicomponent mixture by distillation; each of which has different energy requirements. Here, we classify heat integration (a valuable method of reducing energy requirements) within distillation into two categories: conventional thermal coupling with mass exchange between columns (TCM) and thermal coupling via heat transfer without mass exchange (TCH). The sharp split distillation configurations, with the lowest number of distillation sections and transfer streams, provide simple distillation configurations but are known to have heat duties that are much higher than the fully thermally coupled (FTC) or Petlyuk configuration. However, for a mixture with four or more components, FTC, having the maximum number of column sections, is a complex configuration to build and operate. Through specific examples of four and five component distillations, we present, for the first time, sharp split configurations, using only one TCH and no TCM, which have a lower heat duty than the corresponding FTC containing only TCM, without requiring substantial pressure changes in the system.
Charge-Transfer Versus Charge-Transfer-Like Excitations Revisited
Criteria to assess charge-transfer (CT) and `CT-like' character of electronic excitations are examined. Time-dependent density functional theory (TDDFT) with non-hybrid, hybrid, and tuned long-range corrected (LC) functionals is compared with with coupled-cluster (CC) benchmarks. The test set includes an organic CT complex, two `push-pull' donor-acceptor chromophores, a cyanine dye, and several polycyclic aromatic hydrocarbons. Proper CT is easily identified. Excitations with significant density changes upon excitation within regions of close spatial proximity can also be diagnosed. For such excitations, the use of LC functionals in TDDFT sometimes leads to dramatic improvements of the singlet energies, similar to proper CT, which has led to the concept of `CT-like' excitations. However, `CT-like' excitations are not like charge transfer, and the improvements are not obtained for the right reasons. The triplet excitation energies are underestimated for all systems, often severely. For the `CT-like' candidates, when going from a non-hybrid to an LC functional the error in the singlet-triplet (S/T) separation changes from negative to positive, providing error compensation. For the cyanine, the S/T separation is too large with all functionals, leading to the best error compensation for non-hybrid functionals.
Quantum Confinement and Decoherence Effect on Excited Electron Transfer at the Semiconductor–Molecule Interface: A First-Principles Dynamics Study
Excited electron dynamics at the semiconductor–molecule interface play a vital role in many solar energy conversion applications and beyond. First-principles dynamics simulation is used to study how excited electron dynamics in a type-II semiconductor–molecule interface is affected when the surface of a bulk semiconductor is replaced with that of a quantum dot. In particular, the interface between the hydrogen-terminated silicon(111) surface and a simple organic molecule is investigated. Quantum confinement was found to significantly slow down the excited electron relaxation and the interfacial transfer of the excited electron. Additionally, the role of decoherence was examined. The decoherence affects the dynamics much more significantly for the interface with the quantum dot, while the bulk surface case is affected only marginally by it. Finally, compared to the excited electron relaxation within the quantum dot, the decoherence effect was found to slow down the interfacial transfer from the quantum dot to the molecule by more than an order of magnitude, exhibiting a significant quantum Zeno effect.
Photophysics of J-Aggregate-Mediated Energy Transfer on DNA
Achieving nanoscale spatial and electronic control over the formation of dye aggregates is a major synthetic challenge due to their typically inhomogeneous self-assembly, which limits control over their higher-order organization. To address these challenges, synthetic DNA-templated pseudoisocyanine (PIC) J-aggregates were recently introduced. However, the dependence of the photophysics of the superradiant exciton on the underlying DNA template length and the impact of static disorder on energy transfer through these PIC J-aggregates remain unknown. We examine the delocalization length progression of superradiant PIC excitons by varying the length of poly-A DNA tracts that template PIC J-aggregates. We then investigate the energy-transfer efficiency from PIC J-aggregates with DNA duplex template length, which we found to be limited by static disorder. Furthermore, utilizing the self-assembled and selective formation of superradiant excitons on DNA provides a platform to determine the function of delocalized excitons in the context of nanoscale energy transport.
Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer
The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry breaking charge transfer in polar media. This paper explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem-crossing to produce triplets with ~8 ns time constant (~30% yield) and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ~3 times higher yield than produced via ISC. Furthermore, this high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited state decay for additional charge generation from triplet excited states.
Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer
Ferroelectricity in organic materials remains a subject of great interest, given its potential impact as lightweight information storage media. Here we report supramolecular charge-transfer cocrystals formed by electron acceptor and donor molecules that exhibit ferroelectric behavior along two distinct crystallographic axes. The solid-state superstructure of the cocrystals reveals that a 2:1 ratio of acceptor to donor molecules assemble into nearly orthogonal mixed stacks in which the molecules are positioned for charge-transfer in face-to-face and edge-to-face orientations, held together by an extended hydrogen-bonding network. Polarization hysteresis was observed along the face-to-face and edge-to-face axes at room temperature. The noncentrosymmetric nature of the cocrystals, required to observe ferroelectric behavior, is demonstrated using second harmonic generation measurements. Furthermore, this finding suggests the possibility of designing supramolecular arrays in which organic molecules support multidimensional information storage.