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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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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Ultrafast photochemistry and electron-diffraction spectra in n → (3s) Rydberg excited cyclobutanone resolved at the multireference perturbative level

We study the ultrafast time evolution of cyclobutanone excited to the singlet n → Rydberg state through non-adiabatic surface-hopping simulationsperformed at extended multi-state complete active space second-order perturbation (XMS-CASPT2) level of theory. These dynamics predict relaxation to the ground-state with a timescale of 822 ± 45 fs with minimal involvement of the triplets. The major relaxation path to the ground-state involves a three-state degeneracy region and leads to a variety of fragmented photoproducts. We simulate the resulting time-resolved electron-diffraction spectra, which track the relaxation of the excited state and the formation of various photoproducts in the ground state.

Chemistry↗
DOE OSTI2020

Low-frequency lattice phonons in halide perovskites explain high defect tolerance toward electron-hole recombination

Low-cost solution-based synthesis of metal halide perovskites (MHPs) invariably introduces defects in the system, which could form Shockley-Read-Hall (SRH) electron-hole recombination centers detrimental to solar conversion efficiency. Here, we investigate the nonradiative recombination processes due to native point defects in methylammonium lead halide (MAPbI 3 ) perovskites using ab initio nonadiabatic molecular dynamics within surface-hopping framework. Regardless of whether the defects introduce a shallow or deep band state, we find that charge recombination in MAPbI 3 is not enhanced, contrary to predictions from SRH theory. We demonstrate that this strong tolerance against defects, and hence the breakdown of SRH, arises because the photogenerated carriers are only coupled with low-frequency phonons and electron and hole states overlap weakly. Both factors appreciably decrease the nonadiabatic coupling. We argue that the soft nature of the inorganic lattice with small bulk modulus is key for defect tolerance, and hence, the findings are general to other MHPs.

Science & Technology - Other Topics↗
DOE OSTI2022

Conformer-Specific Dissociation Dynamics in Dimethyl Methylphosphonate Radical Cation

The dynamics of the dimethyl methylphosphonate (DMMP) radical cation after production by strong field adiabatic ionization have been investigated. Pump-probe experiments using strong field 1300 nm pulses to adiabatically ionize DMMP and a 800 nm non-ionizing probe induce coherent oscillations of the parent ion yield with a period of about 45 fs. The yields of two fragments, PO 2 C 2 H 7 + and PO 2 CH 4 + , oscillate approximately out of phase with the parent ion, but with a slight phase shift relative to each other. We use electronic structure theory and nonadiabatic surface hopping dynamics to understand the underlying dynamics. The results show that while the cation oscillates on the ground state along the P=O bond stretch coordinate, the probe excites population to higher electronic states that can lead to fragments PO 2 C 2 H 7 + and PO 2 CH 4 + . The computational results combined with the experimental observations indicate that the two conformers of DMMP that are populated under experimental conditions exhibit different dynamics after being excited to the higher electronic states of the cation leading to different dissociation products. These results highlight the potential usefulness of these pump-probe measurements as a tool to study conformer-specific dynamics in molecules of biological interest.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Exact Factorization Adventures: A Promising Approach for Non-Bound States

Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides potentials that act on the nuclear subsystem or electronic subsystem, which contain the effects of the coupling to the other subsystem in an exact way. We briefly review the various applications of the XF idea in different realms, and how features of these potentials aid in the interpretation of two different laser-driven dissociation mechanisms. We present a detailed study of the different ways the coupling terms in recently-developed XF-based mixed quantum-classical approximations are evaluated, where either truly coupled trajectories, or auxiliary trajectories that mimic the coupling are used, and discuss their effect in both a surface-hopping framework as well as the rigorously-derived coupled-trajectory mixed quantum-classical approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1974

Crossed beam study of the reaction O/+/ + N2 yields NO/+/ + N

The kinematics of the reaction O(+)(4 S) + N2 yields NO(+) + N were studied using crossed molecular beams. Product angular and energy distributions were measured for the initial relative translational energy range from 1.5 to 15.8 eV. The products are formed in their ground electronic states. The product distributions are described, with some deviations, by the spectator stripping model. No evidence was found for a persistent complex or for a second mechanism. A scattering chamber study of 0 deg lab was made of the related reactions 15N(+) + 14NO yields 15N14N(+), 15NO(+), 14NO(+). The results obtained are discussed in terms of possible surface hopping effects.

Smith, G. P. K.↗
DOE OSTI2023

Unusual magnetotransport in twisted bilayer graphene from strain-induced open Fermi surfaces

Anisotropic hopping in a toy Hofstadter model was recently invoked to explain a rich and surprising Landau spectrum measured in twisted bilayer graphene away from the magic angle. Suspecting that such anisotropy could arise from unintended uniaxial strain, we extend the Bistritzer–MacDonald model to include uniaxial heterostrain and present a detailed analysis of its impact on band structure and magnetotransport. We find that such strain strongly influences band structure, shifting the three otherwise-degenerate van Hove points to different energies. Coupled to a Boltzmann magnetotransport calculation, this reproduces previously unexplained nonsaturating B 2 magnetoresistance over broad ranges of density near filling ν = ± 2 and predicts subtler features that had not been noticed in the experimental data. In contrast to these distinctive signatures in longitudinal resistivity, the Hall coefficient is barely influenced by strain, to the extent that it still shows a single sign change on each side of the charge neutrality point—surprisingly, this sign change no longer occurs at a van Hove point. The theory also predicts a marked rotation of the electrical transport principal axes as a function of filling even for fixed strain and for rigid bands. More careful examination of interaction-induced nematic order versus strain effects in twisted bilayer graphene could thus be in order.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Versatile stochastic model for predictive KMC simulation of fcc metal nanostructure evolution with realistic kinetics

Stochastic lattice-gas models provide the natural framework for analysis of the surface diffusion-mediated evolution of crystalline metal nanostructures on the appropriate time scale (often 10 1 –10 4 s) and length scale. Model behavior can be precisely assessed by kinetic Monte Carlo simulation, typically incorporating a rejection-free algorithm to efficiently handle the broad range of Arrhenius rates for hopping of surface atoms. The model should realistically prescribe these rates, or the associated barriers, for a diversity of local surface environments. However, commonly used generic choices for barriers fail, even qualitatively, to simultaneously describe diffusion for different low-index facets, for terrace vs step edge diffusion, etc. We introduce an alternative Unconventional Interaction–Conventional Interaction formalism to prescribe these barriers, which, even with few parameters, can realistically capture most aspects of behavior. Here, the model is illustrated for single-component fcc metal systems, mainly for the case of Ag. It is quite versatile and can be applied to describe both the post-deposition evolution of 2D nanostructures in homoepitaxial thin films (e.g., reshaping and coalescence of 2D islands) and the post-synthesis evolution of 3D nanocrystals (e.g., reshaping of nanocrystals synthesized with various faceted non-equilibrium shapes back to 3D equilibrium Wulff shapes).

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

Influence of tungsten doping on nonradiative electron–hole recombination in monolayer MoSe 2 with Se vacancies

Two-dimensional transition metal dichalcogenides (TMDs) are receiving significant attention due to their excellent electronic and optoelectronic properties. The material quality is greatly affected by defects that are inevitably generated during material synthesis. Focusing on chalcogenide vacancies, which constitute the most common defect, we use the state-of-the-art simulation methodology developed in our group to demonstrate that W doping of MoSe 2 with Se vacancies reduces charge carrier losses by two mechanisms. First, W doping makes the formation of double Se vacancies unfavorable, while it is favorable in undoped MoSe 2 . Second, if a Se vacancy is present, the charge carrier lifetimes are extended in the W-doped MoSe 2 . Combining ab initio real-time time-dependent density functional theory with nonadiabatic molecular dynamics, the simulations show that the nonradiative carrier losses in the presence of Se vacancies proceed by sub-10 ps electron trapping and relaxation down the manifold of trap states, followed by a 100 ps recombination of trapped electrons with free holes. The electron–vibrational energy exchange is driven by both in-plane and out-of-plane vibrational motions of the MoSe 2 layer. Additionally, the atomistic studies advance our understanding of the influence of defects on charge carrier properties in TMDs and guide improvements of material quality and development of TMD applications.

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

Case studies of the time-dependent potential energy surface for dynamics in cavities

Here, the exact time-dependent potential energy surface driving the nuclear dynamics was recently shown to be a useful tool to understand and interpret the coupling of nuclei, electrons, and photons in cavity settings. Here, we provide a detailed analysis of its structure for exactly solvable systems that model two phenomena: cavity-induced suppression of proton-coupled electron-transfer and its dependence on the initial state, and cavity-induced electronic excitation. We demonstrate the inadequacy of simply using a weighted average of polaritonic surfaces to determine the dynamics. Such a weighted average misses a crucial term that redistributes energy between the nuclear and the polaritonic systems, and this term can in fact become a predominant term in determining the nuclear dynamics when several polaritonic surfaces are involved. Evolving an ensemble of classical trajectories on the exact potential energy surface reproduces the nuclear wavepacket quite accurately, while evolving on the weighted polaritonic surface fails after a short period of time. The implications and prospects for application of mixed quantum-classical methods based on this surface are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Non-Kasha fluorescence of pyrene emerges from a dynamic equilibrium between excited states

Pyrene fluorescence after a high-energy electronic excitation exhibits a prominent band shoulder not present after excitation at low energies. The standard assignment of this shoulder as a non-Kasha emission from the second-excited state (S 2 ) has been recently questioned. To elucidate this issue, we simulated the fluorescence of pyrene using two different theoretical approaches based on vertical convolution and nonadiabatic dynamics with nuclear ensembles. To conduct the necessary nonadiabatic dynamics simulations with high-lying electronic states and deal with fluorescence timescales of about 100 ns of this large molecule, we developed new computational protocols. The results from both approaches confirm that the band shoulder is, in fact, due to S 2 emission. We show that the non-Kasha behavior is a dynamic-equilibrium effect not caused by a metastable S 2 minimum. However, it requires considerable vibrational energy, which can only be achieved in collisionless regimes after transitions into highly excited states. This strict condition explains why the S 2 emission was not observed in some experiments.

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

A windowed mean trajectory approximation for condensed phase dynamics

We propose a trajectory-based quasi-classical method for approximating dynamics in condensed phase systems. Building upon the previously developed optimized mean trajectory approximation that has been used to compute linear and nonlinear spectra, we borrow some ideas from filtering trajectory methods to obtain a novel semiclassical method for the dynamical propagation of density matrices. This new approximation is tested rigorously against standard multistate electronic models, spin-boson models, and models of the Fenna–Matthews–Olson complex. For dissipative systems, the current method is significantly better or as good as many other semiclassical methods available, especially at low temperatures and for off-diagonal density matrix elements, whereas for scattering models, the current method bears similar limitations as mean-field propagation schemes. All results are tested against the numerically exact hierarchical equations of motion method. In conclusion, the new method shows excellent agreement across various parameter regimes with numerically exact results, highlighting the robustness and accuracy of our approach.

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

Bio-Inspired Engineering of Exploration Systems

The multidisciplinary concept of "bioinspired engineering of exploration systems" (BEES) is described, which is a guiding principle of the continuing effort to develop biomorphic explorers as reported in a number of articles in the past issues of NASA Tech Briefs. The intent of BEES is to distill from the principles found in successful nature-tested mechanisms of specific crucial functions that are hard to accomplish by conventional methods but that are accomplished rather deftly in nature by biological organisms. The intent is not just to mimic operational mechanisms found in a specific biological organism but to imbibe the salient principles from a variety of diverse bio-organisms for the desired crucial function. Thereby, we can build explorer systems that have specific capabilities endowed beyond nature, as they will possess a combination of the best nature-tested mechanisms for that particular function. The approach consists of selecting a crucial function, for example, flight or some selected aspects of flight, and develop an explorer that combines the principles of those specific attributes as seen in diverse flying species into one artificial entity. This will allow going beyond biology and achieving unprecedented capability and adaptability needed in encountering and exploring what is as yet unknown. A classification of biomorphic flyers into two main classes of surface and aerial explorers is illustrated in the figure, with examples of a variety of biological organisms that provide the inspiration in each respective subclass. Such biomorphic explorers may possess varied mobility modes: surface-roving, burrowing, hopping, hovering, or flying, to accomplish surface, subsurface, and aerial exploration. Preprogrammed for a specific function, they could serve as one-way communicating beacons, spread over the exploration site, autonomously looking for/at the targets of interest. In a hierarchical organization, these biomorphic explorers would report to the next level of exploration mode (say, a large conventional lander/rover) in the vicinity. A widespread and affordable exploration of new/hazardous sites at lower cost and risk would thus become possible by utilizing a faster aerial flyer to cover long ranges and deploying a variety of function- specific, smaller biomorphic explorers for distributed sensing and local sample acquisition. Several conceptual biomorphic missions for planetary and terrestrial exploration applications have been illustrated in "Surface-Launched Explorers for Reconnaissance/ Scouting" (NPO-20871), NASA Tech Briefs, Vol. 26, No. 4 (April, 2002), page 69 and "Bio-Inspired Engineering of Exploration Systems," Journal of Space Mission Architecture, Issue 2, Fall 2000, pages 49-79.

Thakoor, Sanita↗
NASA NTRS1988

To sail the skies of Mars - Scientific ballooning on the red planet

Balloons represent a novel approach to exploring the surface of Mars. One promising aerostat system incorporates a solar-powered balloon as a means of generating diurnally varying lift and so can 'hop' across the surface, obtaining detailed information at a large number of sites. Two important areas of research and testing are underway on solar balloon technology and balloon payload design. The solar balloon concept has been demonstrated on earth, but more work is needed on a 'flyable' version for Mars. Particular attention must be paid to radiation heat transfer and aerodynamic effects. A special 'snake' payload concept has been demonstrated that allows for balloon system traverses of the surface and provides a usable instrument platform. A balloon system of this type could obtain unique surface imaging and physical and chemical data. The flight of the balloon also provides in situ atmospheric boundary-layer and circulation measurements.

Gaidos, Eric J.↗
DOE OSTI2021

Shape Stability of Truncated Octahedral fcc Metal Nanocrystals

Metallic nanocrystals (NCs) can be synthesized with tailored nonequilibrium shapes to enhance desired properties, e.g., octahedral fcc metal NCs optimize catalytic activity associated with {111} facets. However, maintenance of optimized properties requires stability against thermal reshaping. Thus, we analyze the reshaping of truncated fcc metal octahedra mediated by surface diffusion using a stochastic atomistic-level model with energetic input parameters for Pd. Furthermore, the model describes NC thermodynamics by an effective nearest-neighbor interaction and includes a realistic treatment of diffusive hopping for undercoordinated surface atoms. Kinetic Monte Carlo simulation reveals that the effective barrier, E eff , for the initial stage of reshaping is strongly tied to the degree of truncation of the vertices in the synthesized initial octahedral shapes. This feature is elucidated via exact analytic determination of the energy variation along the optimal reshaping pathway at low-temperature (T), which involves transfer of atoms from truncated {100} vertex facets to form new layers on {111} side facets. Deviations from predictions of the low-T analysis due to entropic effects are more prominent for higher T and larger NC sizes.

36 MATERIALS SCIENCE↗
NASA NTRSDate not supplied

Design of a Radioisotope Heat Exchanger Rocket

The state of planetary exploration vehicle technology has become increasingly more advanced over its long history. Better technologies enable more detailed scientific research to be conducted during the vehicle’s life, while advanced manufacturing strategies allow the vehicles to operate for greater lengths of time. However, one aspect of these vehicles has remained constant: the means of exploration. Previous vehicles have all relied on wheels to traverse the surface of the explored planet, limiting their range. The Mars Opportunity Rover, the longest operating rover, only traveled 45.15 km over its life. The radioisotope heat exchanger rocket is a new vehicle concept, designed to use heated gas as a means of propellant. The vehicle collects gas from the surface of a body, stores it in a heated tank, and passes it through a heat exchanger. This process significantly increases the temperature of the collected gas, allowing it to exit through a nozzle with high velocity and efficiency. This process will enable the vehicle to hop across the surface of the body and repeatedly refuel, with the potential of travelling thousands of kilometers during its lifetime. A computer model was constructed to simulate the heat exchanger and nozzle of this proposed system. This simulation allowed the heat exchanger and propellant tank properties to be optimized for the current mission parameters: the exploration of Triton. The nitrogen flows through a 25 kg lithium heat exchanger, consisting of 540, 1.5-mm diameter, 40-cm long Titanium Zirconium Molybdenum pipes, to three operating nozzles. Once landed, the vehicle will conduct science and refueling operations for six days before hopping again. With the optimized design determined from the simulations conducted in this paper, 235.26 kg of nitrogen is collected and stored in a 300 K, 3000 psia tank. With these parameters, a potential hop distance of 39 km with an average specific impulse of 127.5 s is attained. A previous iteration of this vehicle did not include a heat exchanger, instead heating 100 kg of nitrogen to 300 K, only allowing the vehicle to hop 5 km and with a low specific impulse of 60 s. Thus, the addition of the heat exchanger component of the vehicle is shown to potentially double the specific impulse and quadruple the hop distance compared to the previous design.

Thomas E. O'Brien↗