Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “transfer”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Structural Gating Enhances Long-Distance Light-Driven Interfacial Electron Transfer

Structural gating provides a molecular means to transfer electrons preferentially in one desired vectorial direction, a behavior needed for applications in artificial photosynthesis. At the interfaces utilized herein, visible-light absorption by a transition metal complex opens a “structural gate” by planarization of otherwise rotating phenyl rings in p-phenylene ethynylene (PE) bridge units. Planarization provides a conjugated pathway for electron flow toward a conductive oxide surface. Interfacial electron transfer to the oxide restores rotation and closes the gate to the unwanted recombination reaction. This structural gating results in nearly quantitative long-distance (>20 Å) interfacial electron transfer that occurs ~1000 times faster than transfer in the opposite direction. A comparative kinetic study of these complexes with those that contain ionic bridge units, without gating function, as a function of the applied potential and hence –ΔG° provided a physical basis for the structural gating. A small distance-dependent reorganization energy with weak electronic coupling underlies the success of this gate that enables efficient long-distance electron transfer and slow recombination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Multisite Proton–Coupled Electron Transfer at a Keggin-Type Polyoxotungstate

Proton−coupled electron transfer (PCET) governs many redox transformations, but is thermodynamically constrained when proton and electron transfer occur at a single site. Here, we introduce a new multisite PCET (MSPCET) platform, based on the Keggin-type polyoxotungstate, [VW 12 O 40 ] 3− (VW 12 ). Pairing VW 12 with either Brønsted bases or acids yields reagent pairs with tunable effective bond dissociation free energies (BDFE eff ) over 15 kcal mol −1 , enabling both oxidative and reductive H atom transfer reactions. Kinetic studies on the oxidative pathway by using 2,4,6- t Bu 3 PhOH as a model hydrogen atom (H atom) donor reveal a product-like, entropy-dominated concerted proton−electron transfer (CPET) pathway from a preorganized hydrogen-bonded complex. By contrast, reductive H atom transfer reactions exhibit larger ΔH ‡ values, measurable kinetic isotope effects, and balanced Brønsted slope, consistent with synchronous CPET-type mechanism. Extension to N−H, O−H, and C−H substrates demonstrates the versatility of the VW 12 MS-PCET platform for tunable (de)hydrogenation.

Charge transfer↗
DOE OSTI2025

Convective heat transfer enhancement through additively built multiscale micro-tetrahedron features

Use of Additive Manufacturing (AM) to improve the heat transfer characteristics of tip shrouds in high-pressure turbines is being considered by industries. Existing designs of these components integrate micro-cooling channels to reduce the bulk temperature for improved life. In this research, closely packed micro tetrahedron features in addition to AM roughness has been considered. Further, this multiscale surface characteristics increased surface area per unit volume available for heat exchange. Micro-tet features were designed, manufactured, characterized, and evaluated systematically while increasing their height. An enormous increase in the overall wetted surface area by 200 % was measured. The convective heat transfer enhancement was ~3.72 times EDM rough coupon, and friction factor enhancement was ~5.5 times EDM rough coupon. Furthermore, the proposed design offers 2.5 times enhanced heat transfer for a given 2 W pumping power compared to our EDM rough coupon. Heat transfer enhancement was observed to not vary strongly with increased Reynolds number. Such complex designs are only possible through additive manufacturing for increased heat transfer with little pressure penalty. Finally, increasing the micro-tet height for increased surface area and improved heat exchange beyond an upper limit might not be a significant benefit as it gets compensated by increasing skin friction.

42 ENGINEERING↗
DOE OSTI2025

Enhanced pool boiling heat transfer using novel inverted trapezoid microgroove structures

Pool boiling heat transfer improvements with enhanced surfaces have been extensively studied for various hydrofluorocarbon (HFC) refrigerants. However, there is a limited number of studies in the open literature that focus on the pool boiling heat transfer characteristics of hydrofluoroolefin (HFO) refrigerants on enhanced surfaces. This study aims to address this gap by analyzing the pool boiling behavior of HFO refrigerants, specifically R1234yf and R1234ze(E). Experiments were conducted on both plain surfaces and novel inverted trapezoid microgroove structures. Further, the experimental results indicate that the microgroove structures can improve heat transfer coefficients by up to 80% compared to plain surfaces. Additionally, the performance of R1234yf and R1234ze(E) was compared to that of R134. It was observed that R1234yf exhibited comparable performance to R134a, while R1234ze(E) showed slightly lower performance. To assess the influence of saturation temperature on pool boiling heat transfer, tests were conducted at different saturation temperatures of 15℃, 25℃, and 35℃. The findings revealed that the pool boiling heat transfer coefficient increases with rising saturation temperature.

42 ENGINEERING↗
DOE OSTI2025

Efficient Size-Dependent Hot Electron Transfer from Au to TiO 2 Nanoparticles

Harvesting of plasmon-induced hot carriers at the metal/semiconductor interface offers a promising and innovative avenue for solar energy conversion. However, their practical implementation is often hampered by their limited efficiencies. Herein, we have demonstrated a highly efficient plasmonic hot electron transfer with a quantum efficiency (QE) of up to 57 ± 4% from 5.25 nm Au nanoparticles (NPs) to TiO 2 films under 400 nm ultrafast laser excitation. The observed hot electron transfer QEs decrease at larger particle sizes, to 20% for 9.1 nm Au, and show negligible changes with excitation wavelengths at 400, 500, and 600 nm. Analysis of the size and excitation wavelength dependent hot electron transfer QEs suggests they contain contributions of interband absorption, indirect plasmon-induced hot electron transfer (PHET), and direct plasmon-induced interfacial charge transfer transition (PICTT) pathways, and QEs of all three pathways increase at smaller Au size. Our result suggests that reducing plasmon particle sizes is a promising approach for efficient plasmonic hot-carrier extraction.

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

Pressure-Modulated Energy Transfer Dynamics in Mn 2+ -Doped CdS/ZnS Core/Shell Quantum Dots

Transition metal doping in semiconductor quantum dots (QDs) significantly impacts their optical properties, thus expanding the range of their potential optoelectronic applications. This study investigates the pressure-dependent energy transfer dynamics in Mn 2+ -doped CdS/ZnS core/shell QDs, focusing on how external hydrostatic pressure modulates these dynamics and optical properties. By synthesizing Mn 2+ -doped QDs with varying Mn 2+ doping concentrations, we explore the effects of the pressure on photoluminescence (PL) spectra and energy transfer efficiency. Our study reveals that increasing pressure induces a blueshift in the QD host bandgap PL and a redshift in the Mn 2+ dopant PL. The pressure-induced shifts highlight a unique modulation mechanism where the energy transfer efficiency decreases with pressure due to reduced wave function overlap between host excitons and Mn 2+ dopants. Detailed analysis of the PL quantum yields and energy transfer rate constants provides insights into these dynamics, suggesting that the pressure can effectively and reversibly regulate the energy transfer efficiencies and rates. In conclusion, these results have implications for developing pressure-sensitive configurable devices and exploring pressure-induced phenomena in doped nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, Are Intrinsically Correlated to the Structural Disorder

Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pK a or band gaps (E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.

Bond dissociation free energy↗
DOE OSTI2026

Ultrafast Proton-Coupled Electron Transfer Reactions at Unit Quantum Yield

Proton-coupled electron transfer (PCET) reactions mediate essential biological energy-conversion processes, yet dynamical experiments that distinguish concerted electron/proton motion from sequential electron-transfer/proton-transfer pathways are unprecedented on ultrafast time scales. Here we report a tightly coupled donor–spacer–acceptor assembly, NDI-Sp-PhOH/BI, that enables direct interrogation of light-triggered and ultrafast PCET dynamics. Photoexcitation of the naphthalene diimide chromophore drives charge separation forming NDI radical anion and benzimidazolium phenoxy radical (PhO●/BIH+) products with a 440 fs time constant, followed by thermal charge recombination on a 5 ps time scale. Transient visible/near-infrared and mid-infrared spectroscopies independently track electron and proton motion and reveal coincident formation and decay of the charge-separated PCET products, excluding detectable phenol radical cation or phenoxide intermediates expected for sequential electron transfer-proton transfer (ET-PT) pathways. Surface-hopping quasiclassical trajectory simulations demonstrate rapid proton relocation coupled to evolution from locally excited to charge-transfer states, congruent with a concerted mechanism. These combined spectroscopic and computational results establish NDI-Sp-PhOH/BI as an archetype for ultrafast, concerted PCET occurring with unit quantum yield; further, because this platform provides distinct electronic and vibrational spectroscopic handles in its ground, electronically excited, and charge-separated states, it provides new opportunities to characterize mechanistic crossover in biomimetic PCET systems.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer

The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.

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

Simulations of Heat Transfer Using Tight-Fitting Twisted Tape Inserts for First Wall Cooling in Molten Salt Breeder Blankets

One of the major components in fusion energy systems is the fusion blanket, which has a vacuum vessel to contain the plasma. As part of the fusion blanket/vacuum vessel, the first wall and plasma-facing components require sufficient cooling to prevent material degradation during operation from the superheated plasma. Most fusion blanket concepts involve first wall and divertor coolant channels with heat transfer enhancements (HTEs) that are intended to withstand the incident high heat fluxes of 1 to 5 MW/m 2 . Twisted tape inserts are a proposed HTE that have been investigated previously for first wall cooling and monoblock divertor cooling channels and in other nonfusion heat transfer components. By inserting twisted tapes into straight pipes, the amount of turbulence in the system can be increased at lower Reynolds numbers by swirling the flow. This results in better heat transfer characteristics with marginal increases in frictional pressure losses. In particular, simulations of high-Prandtl-number fluids such as the proposed molten salt FLiBe in twisted tapes, which is prototypic to liquid immersion blankets, have not been previously explored. Here, in this study, we simulate various Prandtl numbers in pipes with twisted tape inserts using large eddy simulations to determine the effects of increasing Prandtl numbers on heat transfer performance. The quantities of particular interest are the Nusselt number and the friction factor, which were recovered using data reduction techniques to determine impacts on heat transfer and pressure losses. This work serves as a starting point for determining the feasibility of twisted tape inserts for liquid immersion blanket concepts.

LES↗
DOE OSTI2024

Quest for Cooper Pair Transfer in Heavy-Ion Reactions: The 206 Pb + 118 Sn Case

In this Letter we report on effects of nucleon-nucleon correlations probed in nucleon transfer reactions with heavy ions. We measured with high efficiency and resolution a complete set of observables for neutron transfer channels in the ²⁰⁶Pb + ¹¹⁸Sn system employing a large solid angle magnetic spectrometer, which allowed us to study a wide range of internuclear distances via a detailed excitation function. The coupled channel theory, based on an independent particle transfer mechanism, follows the experimental transfer probabilities for one- and two-neutron pick-up and stripping channels. The experimental two-neutron transfer cross sections indicate that in reactions between pair-vibrational (closed shell) and pair-rotational (open shell) nuclei, correlations manifest via pair-addition and pair-removal modes, which constitute one of the elementary modes of excitations in nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Can Charge Transfer Across C─H⋅⋅⋅O Hydrogen Bonds Stabilize Oil Droplets in Water?

Oil-water emulsions resist aggregation due to the presence of negative charges at their surface that leads to mutual repulsion between droplets, but the molecular origin of oil charge is currently under debate. Although much evidence has suggested that ionic species must accumulate at the interface, an alternative perspective attributes the negative charge on the oil droplet to charge transfer of electron density from water to oil molecules. Although the charge transfer mechanism is consistent with the correct sign of oil charge, it is just as important to provide good estimates of the charge magnitude to explain emulsion stability and electrophoresis experiments. Here, we show using energy decomposition analysis that the amount of net flow of charge from water to oil is negligibly small due to nearly equal forward and backward charge transfer through weak oil-water interactions, such that oil droplets would be unstable and coalesce, contrary to experiment. The lack of charge transfer also explains why vibrational sum frequency scattering reports a blue shift in the oil C-H frequency when forming emulsions with water, which arises from Pauli repulsion due to localized confinement at the interface. Finally, unlike ions, neither charge transfer nor dynamic polarization can produce a finite conductivity needed to couple to electric fields that would explain electrophoretic mobility.

Zhao, Ruoqi↗
DOE OSTI2025

Local heat transfer measurement in a volumetrically heated TPMS lattice using distributed optical fiber thermal sensing

As additive manufacturing continues to reduce design constraints on heat exchange geometries, methods for high-fidelity local heat transfer measurements in nonconventional channel geometries are critical to their continued development. This study presents a novel method for measuring local heat transfer performance in volumetrically heated lattices using a distributed optical fiber temperature sensor. A diamond-type triply periodic minimal surface (TPMS) lattice, 3D-printed from a conductive polymer, was Joule heated while it was convectively cooled with air. Temperature measurements were taken at the solid–fluid interface across 14 internal locations using a single optical fiber over the Reynolds number range 800–2750. The TPMS lattice achieved up to 312% higher heat transfer coefficients compared to developing flow in a straight tube. A Nusselt number correlation was developed for the diamond TPMS, which showed good agreement with data collected for comparable geometries available in literature. In conclusion, this study presents a robust and new method for experimental measurement of the heat transfer coefficient in complex geometries and helps to understand and quantify the exceptional performance of TPMS heat transfer geometries.

TPMS↗
DOE OSTI2026

Edge dislocation mediated anomalous charge transfer in face centered cubic high entropy alloys

The charge transfer in alloys dictates their structural and functional properties. The presence of the line defect can influence the charge transfer characteristics in alloys. The edge dislocation-volume misfit interaction in high entropy alloys is a critical area of interest concerning the development of accurate solid solution strengthening models for these materials. The evolution of the volume misfit of atoms is either studied empirically using Vegard's law or mechanistically using \emph{ab initio} calculations, without considering the effect of edge dislocation on charge transfer explicitly. In this work, we show the influence of edge dislocation on the charge transfer in CoCrFeMnNi, CoCrNi and CoNi using large-scale \emph{ab initio} calculations. The anomalous charge transfer characteristics, in terms of deviations from electronegativity trends, are demonstrated, which are dictated by electronegativity equalisation rather than pair-atom interactions. The deviation of atomic volume in the compressive and tensile stress regions of the edge dislocation is rationalised in terms of anomalous magneto-volume fluctuations in such alloys.

Ghosh, Swarnava [ORNL] (ORCID:0000000338005264)↗
DOE OSTI2025

Quantum simulation of charge and exciton transfer in multi-mode models using engineered reservoirs

Quantum simulation enables studies of open-system dynamics in non-perturbative regimes by programming electronic, vibrational, and environmental interactions on comparable energy scales. Trapped ions offer this capability, combining spins, phonons, and tunable dissipation on one platform. We demonstrate an open-system quantum simulation of charge and exciton transfer in a multi-mode linear vibronic coupling model. Using tailored spin-phonon interactions with reservoir engineering, we emulate a system with two dissipative vibrational modes coupled to donor and acceptor sites and track its non-equilibrium dynamics. We continuously tune the system from the charge transfer regime to the vibrationally assisted exciton transfer regime and find that degenerate modes enhance transfer rates at large energy gaps, while non-degenerate modes activate pathways that reduce the energy-gap dependence. Thus, the presence of one additional vibration introduces interfering pathways and reshapes non-perturbative excitation transfer. Our results establish a scalable, hardware-efficient route to simulate vibronic processes with engineered environments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Revealing ultrafast proton-transfer-mediated autoionization as a source of low-energy electrons in hydrogen-bonded systems

Ionizing radiation can trigger ultrafast proton transfer, a central mechanism in many chemical and biological functions, that in turn can enable or suppress electron relaxation processes and consequently cause abrupt changes in the reaction pathway. This study combines theory and experiment to probe ultrafast relaxation and dissociation in water dimers following inner- and outer-valence photoionization. By tracking electron and nuclear motion simultaneously, we reveal competing fragmentation pathways that produce low-energy electrons, which are key agents in radiation-induced chemistry, including DNA damage. While low-energy electrons are known to arise via intermolecular Coulombic decay, here we identify a faster relaxation mechanism gated by proton transfer following inner-valence ionization, which we call proton-transfer-mediated autoionization. Occurring within 10 femtoseconds, this process alters fragmentation outcomes, yielding either D 3 O + + OD + or D 2 O + + D 2 O + , depending on the interplay of proton migration and hydrogen back-transfer. Our findings underscore the intricate coupling between electronic and nuclear dynamics in hydrogen-bonded systems and establish proton-transfer-mediated autoionization as a significant pathway for low-energy electron generation.

Atomic and molecular interactions with photons↗
DOE OSTI2025

Solvation governs cation transference in glyme-based lithium battery electrolytes

The efficacy of electrochemical systems is governed by the cation transference number, which represents the fraction of current carried by the working ion. Energy is wasted when field-induced motion also drives anions and solvent molecules, decreasing the transference number to near-zero. We present a systematic study of cation transference in a series of electrolytes: tetraglyme (TG), octaglyme (OG), and poly(ethylene oxide) (PEO) mixed with lithium bis(trifluoromethanesulfonyl)imide. In all three electrolytes, starting from the dilute salt concentration limit, the experimentally measured cation transference number decreases with increasing concentration, reaching a minimum between -0.1 and -0.2, before rising back to positive values. Explicit measurements of field-induced species' velocities by electrophoretic nuclear magnetic resonance indicate that negative cation transference numbers in TG and OG electrolytes are dictated by solvation interactions with minimal contribution from anion-cation interactions. Simulation-based solvation structures indicate that OG serves as a bridge between TG and PEO. Multi-charge positive clusters, which are negligible in TG, become increasingly important at higher chain lengths (OG and PEO). As migrating cations drag their solvation shells, this solvation-induced motion is amplified in glyme electrolytes because of covalent interactions between solvating glyme molecules and free glyme molecules.

Im, Julia↗