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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 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

The UV Photoinduced Ring-Closing Reaction of Cyclopentadiene Probed with Ultrafast Electron Diffraction

Conjugated cyclic organic molecules are common across many fields such as pharmaceuticals, are naturally occurring in biological systems, and are used in synthetic materials. One particular area of interest from a photochemical point of view is the formation of highly strained cyclic organics. We investigate the photoinduced reaction of cyclopentadiene, a five-membered organic ring molecule which can form strained three and four carbon rings after photoexcitation with UV light, with the gas-phase ultrafast electron diffraction instrument at the SLAC MeV-UED facility. Electron diffraction offers a direct probe sensitive to the nuclear geometry during the reaction, allowing for the determination of the distribution of products formed following photoexcitation. We observe the simultaneous formation of the highly strained ring- closed bicyclo[2.1.0]pentene and vibrationally hot cyclopentadiene within the temporal resolution of the experiment, and determine the relative yield of all reaction products. Furthermore, the experimental results are in good agreement with the predictions of trajectory simulations.

Computational Chemistry↗
DOE OSTI2020

Ultrafast Spin Crossover in a Room-Temperature Ferrimagnet: Element-Specific Spin Dynamics in Photoexcited Cobalt Ferrite

Transition metal complexes capable of photoinduced spin crossover have been greatly investigated because of their potential to enable ultrafast optical control of information processing. Yet, any real application of photoswitchable molecules requires that spin crossover be paired with additional functionality such as long-range magnetic order. Important advances combining these functions are notably reported for a number of bimetallic Prussian Blue analogues; however, to date, PBA-based magnetic photoswitches can only operate below 150 K due to loss of magnetic order. In contrast, cobalt ferrite is a ferrimagnetic semiconductor with a Curie temperature of 790 K and extremely favorable magnetic properties by comparison to state-of-the-art PBAs. The mixed valence electronic structure of cobalt ferrite is reminiscent of cobalt–iron PBA, which is a well-known photoswitch. To investigate the potential for photoswitching in this material, we employ transient XUV spectroscopy to probe charge and spin dynamics with element-specific resolution on the femtosecond time scale. Results show that 400 nm light excites a metal-to-metal charge transfer transition, which drives the crossover of high-spin Co 2+ to low-spin Co 3+ with a time constant of 405 ± 29 fs and an internal quantum efficiency of unity. This result establishes the existence of efficient photoswitching in a new class of robust ferrimagnetic spinel ferrites.

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

Ultrafast Charge Transfer Dynamics at the Origin of Photoconductivity in Doped Organic Solids

In spite of their growing importance for optoelectronic devices, the fundamental properties and photophysics of molecularly doped organic solids remain poorly understood. Such doping typically leads to a small fraction of free conductive charges, with most electronic carriers remaining Coulombically bound to the ionized dopant. Recently, we have reported photocurrent for devices containing vacuum-deposited TAPC (1,1-bis(4-bis(4- methylphenyl)aminophenyl)cyclohexane) doped with MoO 3 , showing that photoexcitation of charged TAPC molecules increases the concentration of free holes that contribute to conduction. Here, we elucidate the excited-state dynamics of such doped TAPC films to unravel the key mechanisms responsible for this effect. We demonstrate that excitation of different electronic transitions in charged and neutral TAPC molecules allows bound holes to overcome the Coulombic attraction to their MoO 3 counterions, resulting in an enhanced yield of long-lived free carriers. This is caused by ultrafast back-and-forth shuffling of charges and excitation energy between adjacent cations and neutral molecules, competing with relatively slow nonradiative decay from higher excited states of TAPC •+ . The light-induced generation of conductive carriers requires the coexistence of cationic and neutral TAPC, a favorable energy level alignment, and intermolecular interactions in the solid state.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ultrafast Collective Excited-State Dynamics of a Virus-Supported Fluorophore Antenna

Radiation brightening was recently observed in a multifluorophore-conjugated brome mosaic virus (BMV) particle at room temperature under pulsed excitation. On the basis of its nonlinear dependence on the number of chromophores, the origins of the phenomenon were attributed to a collective relaxation. However, the mechanism remains unknown. Here, we present ultrafast transient absorption and fluorescence spectroscopic studies which shed new light on the collective nature of the relaxation dynamics in such radiation-brightened, multifluorophore particles. Our findings indicate that the emission dynamics is consistent with a superradiance mechanism. The ratio between the rates of competing radiative and nonradiative relaxation pathways depends on the number of chromophores per virus. The findings suggest that small icosahedral virus shells provide a unique biological scaffold for developing nonclassical, deep subwavelength light sources and may open new avenues for the development of photonic probes for medical imaging applications.

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

Ultrafast Dynamics and Rearrangement of the EUV Photoacid Generator Phenyl Triflate

Extreme UV photolithography is a high-energy process crucial for modern computer chip fabrication, where photoacid generators (PAGs) enhance radiation exposure by producing reactive chemical species. This study investigates the ultrafast dissociative dynamics of phenyl triflate, a widely used PAG, under high-energy ionizing conditions. The dissociative ionization of the phenyl triflate cation, which includes a molecular rearrangement that releases SO 2 and forms the phenyl trifluoromethyl ether cation, is measured over the first 5 ps. These dynamics reveal vibrational coherence corresponding to a torsional mode of the cation, involving the twisting of the phenyl group into the O–S–C plane. Electronic structure calculations for the radical cation are in good agreement with the experimentally observed vibrational coherence. These findings provide valuable insights into the behavior of phenyl triflate under ionizing conditions similar to its industrial usage.

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

Characterizing Ultrafast Intersystem Crossing Pathways in Molecular Pt Dimers Using Time-Resolved Wide-Angle X-ray Scattering

Vibronic coupling between transition metal charge transfer states is a potential mechanism for enhancing the intersystem crossing (ISC) rate. Vibronic coupling-driven ISC has been observed in Pt­(II) dimer complexes, where the trajectory across excited-state pathways is tuned by atomic displacements via Pt–Pt stretching vibrations. Time-resolved wide-angle X-ray scattering (TR-WAXS) was utilized to quantify the Pt–Pt contraction following metal–metal-to-ligand charge transfer (MMLCT) excitation in Pt dimers with different bridging ligands. Both complexes exhibit Pt–Pt bond formation with a decrease in Pt–Pt distance of ∼ 0.25 Å and coherent vibrational wavepackets (CVWPs) encoded in the Pt–Pt contraction of both dimers. However, the complexes exhibit different time-dependent evolution of their CVWPs. Analysis of interference patterns between different CVWPs is used to track the trajectory across the excited-state surfaces. Furthermore, this work demonstrates that the interference between CVWPs in ultrafast TR-WAXS encodes indirect information regarding electronic excited-states to reveal the Pt dimer bridge-dependent ISC mechanism.

Computational chemistry↗
DOE OSTI2025

The Effects of Shockwave Pressures on Ultrafast Vibrational Energy Transfer in BNFF, a Hydrogen-Free Energetic Material

Energy conversion in energetic materials from shock-wave-induced lattice compression to bond breaking critically depends on vibrational coupling and energy transfer between intra- and intermolecular vibrations, though the details of the mechanisms remain unknown. Herein, we indirectly tune the strength of intermolecular interactions in 3,4-bis(3-nitrofurazan-4-yl)furoxan (BNFF), a hydrogen-free energetic material characterized by van der Waals interactions, by applying high static pressure using a diamond anvil cell and monitoring vibrational energy transfer (VET) with ultrafast broadband infrared pump–probe spectroscopy. As BNFF is compressed from ambient pressure to 9 GPa, we find that VET accelerates by ∼ 0.9 ps/GPa. Density functional theory is applied in tandem with experiments to assign mode character and elucidate VET pathways. In conclusion, we find that furazan ring O–N–O vibrations, which are high-frequency detonation-relevant vibrational modes, experience increased sensitivity to lattice compression under shockwave pressures. These findings provide new mechanistic insight into how intermolecular interactions govern the rate and selectivity of VET.

Energy transfer↗
DOE OSTI2026

Resolving Competing Ultraviolet Photoinduced Ring-Opening and Dissociation Pathways in Iodothiophenes by Ultrafast Electron Diffraction

The ultraviolet photochemistry of halothiophenes is thought to proceed via competing pathways, prompt C–X (X = halogen) bond fission, and parent ring opening followed by fragmentation, yet direct structural evidence distinguishing these mechanisms is limited. Here, time-resolved gas-phase ultrafast electron diffraction (UED) has been used to directly follow the structural dynamics of 2- and 3-iodothiophene following photoexcitation at 247 nm. For both isomers, the time-resolved pair distribution functions reveal the appearance of new interatomic distances that cannot be explained by simple C–I bond cleavage and formation of C 4 SH 3 radical cofragments. The signatures, particularly those for 2-iodothiophene, are consistent with a rival ring-opening channel of the intact parent, which evolve on time scales distinct from those associated with the direct C–I bond cleavage. In addition, the extracted kinetics indicate that the ring-opening channel occurs faster in 2-iodothiophene than in the 3-isomer at this excitation wavelength. Furthermore, these measurements provide direct geometric evidence for competing pathways leading to different structures following photodissociation in a model heteroaromatic and further establish UED as a sensitive probe of complex excited-state chemistry.

Bond cleavage↗
DOE OSTI2023

Ultrafast Optical Nanoscopy of Carrier Dynamics in Silicon Nanowires

Carrier distribution and dynamics in semiconductor materials often govern their physical properties that are critical to functionalities and performance in industrial applications. The continued miniaturization of electronic and photonic devices calls for tools to probe carrier behavior in semiconductors simultaneously at the picosecond time and nanometer length scales. Here, in this paper, we report pump–probe optical nanoscopy in the visible-near-infrared spectral region to characterize the carrier dynamics in silicon nanostructures. By coupling experiments with the point-dipole model, we resolve the size-dependent photoexcited carrier lifetime in individual silicon nanowires. We further demonstrate local carrier decay time mapping in silicon nanostructures with a sub-50 nm spatial resolution. Our study enables the nanoimaging of ultrafast carrier kinetics, which will find promising applications in the future design of a broad range of electronic, photonic, and optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Plasmonic Diamond Membranes for Ultrafast Silicon Vacancy Emission

Silicon vacancy centers (SiVs) in diamond have emerged as a promising platform for quantum sciences due to their excellent photostability, minimal spectral diffusion, and substantial zero-phonon line emission. However, enhancing their slow nanosecond excited-state lifetime by coupling to optical cavities remains an outstanding challenge, as current demonstrations are limited to ~10-fold. Here, we couple negatively charged SiVs to sub-diffraction-limited plasmonic cavities and achieve an instrument-limited ≤8 ps lifetime, corresponding to a 135-fold spontaneous emission rate enhancement and a 19-fold photoluminescence enhancement. Nanoparticles are printed on ultrathin diamond membranes on gold films which create arrays of plasmonic nanogap cavities with ultrasmall volumes. SiVs implanted at 5 and 10 nm depths are examined to elucidate surface effects on their lifetime and brightness. The interplay between cavity, implantation depth, and ultrathin diamond membranes provides insights into generating ultrafast, bright SiV emission for next-generation diamond devices.

Purcell enhancement↗
DOE OSTI2021

Ultrafast Interlayer Charge Transfer between Bilayer PtSe 2 and Monolayer WS 2

Interlayer charge transfer (CT) between PtSe 2 and WS 2 is studied experimentally. Layer-selective pump–probe and photoluminescence quenching measurements reveal ultrafast interlayer CT in the heterostructure formed by bilayer PtSe 2 and monolayer WS 2 , confirming its type-II band alignment. The CT facilitates the formation of the interlayer excitons with a lifetime of several hundred ps to 1 ns, a diffusion coefficient of 0.9 cm 2 s –1 , and a diffusion length reaching 200 nm. Furthermore, these results demonstrate the integration of PtSe 2 with other materials in van der Waals heterostructures with novel charge-transfer properties and help develop fundamental understanding on the performance of various optoelectronic devices based on heterostructures involving PtSe 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ultrafast Triplet Generation at the Lead Halide Perovskite/Rubrene Interface

Triplet sensitization of rubrene by bulk lead halide perovskites has recently resulted in efficient infrared-to-visible photon upconversion via triplet-triplet annihilation. Notably, this process can occur under solar relevant fluxes, potentially paving the way toward integration with photovoltaic devices. In order to further improve the upconversion efficiency, the fundamental photophysical pathways at the perovskite/rubrene interface must be clearly understood to maximize charge extraction. Here, we utilize ultrafast transient absorption spectroscopy to elucidate the processes underlying triplet generation at the perovskite/rubrene interface. In this work, our results point to a triplet generation mechanism based on hot carriers; thermally excited charge carriers in the perovskite cool more rapidly in the presence of rubrene, suggesting rapid extraction of these thermally excited carriers on the picosecond time scale. Subsequent triplet formation in rubrene is observed on a subnanosecond time scale.

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

Ultrafast Reaction Mechanisms in Perovskite Based Photocatalytic C–C Coupling

Solar driven carbon-carbon (C-C) bond formation is a new direction in solar energy utilization. Earth abundant nanocrystal based photocatalysts are highly sought after as they can potentially eliminate expensive noble metal catalysts. A detailed understanding of the underlying reaction mechanisms could provide guidance in designing new systems that can activate a larger class of small molecules. Here, we employ transient absorption spectroscopy to study a model C-C bond formation reaction, i.e., a-alkylation of aldehydes catalyzed by colloidal CsPbBr3 nanocrystals (NCs). We find that both electrons and holes undergo ultrafast charge transfer (~50 ps) from photoexcited perovskite NCs to reactant molecules. A charge separated state lives for more than 0.8 µs, enabling a radical mechanism to form the C-C bonds. We discuss the differences between the NCs photoredox catalysts and the molecular catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ultrafast Carrier Drift Transport Dynamics in CsPbI3 Perovskite Nanocrystalline Thin Films

We study the early time carrier drift dynamics in CsPbI3 nanocrystal thin films with a sub 25 ps time resolution. Prior to trapping, carriers exhibit band-like transport characteristics, which is similar to those of traditional semiconductor solar absorbers including Si and GaAs due to optical phonon and carrier scattering at high temperatures. In contrast to the popular polaron scattering mechanism, the CsPbI3 nanocrystal thin film demonstrates the strongest optical phonon scattering mechanism among other inorganic-organic hybrid perovskites, Si, and GaAs. This ultrafast dynamics study establishes a foundation for understanding the fundamental carrier drift properties that drive perovskite nanocrystal optoelectronics.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,S↗
DOE OSTI2025

Construction of MoS 2 /MoO 3 Heterostructure with Ultrafast-Charged and Superior Low-Temperature Sodium Storage Properties

The electrochemical reaction kinetics of sodium-ion batteries (SIBs) become sluggish at low temperatures, resulting in significant reductions in energy density and power density. Rational design of anode materials with excellent low-temperature performance is of great significance for promoting the application of SIBs under extreme conditions. Here, in this study, the spontaneous hydrolysis and oxidation reactions of MoS 2 in aqueous solution are used to successfully construct the MoS 2 /MoO 3 heterostructure. The formation of built-in electric fields at the MoS 2 /MoO 3 heterointerfaces improves the electrochemical reaction kinetics, thereby enhancing the rate performance. In addition, the dual-phase material can effectively buffer the volume strain during the cycle process, thereby improving the cycle stability. Thus, the MoS 2 /MoO 3 displays ultrafast charging properties at room temperature (up to 244.6 mAh g –1 at 40 A g –1 , discharge/charge in 22 s). Even at −40 °C, it also exhibits a high capacity of 303.7 mAh g –1 and superior cycling performance (capacity retention rate up to 92.9% after 900 cycles at 2 A g –1 ).

MoS2↗
DOE OSTI2026

Ultrafast Nanoimaging of Carrier Funneling in Composition-Graded Semiconductor Nanowires

Recent advances in bandgap engineering of low-dimensional semiconductors have enabled high-efficiency carrier transport in miniaturized electronic and optoelectronic devices. The physical properties and functionalities of these materials are governed by complex carrier dynamics coupled with multiple transport mechanisms in tailored band structures. Here, we report ultrafast nanoimaging of carrier funneling and recombination in composition-grade CdSxSe1-x nanowires using pump-probe near-field nanoscopy. Leveraging the high resolution of this technique in both space and time, we resolve nanoscale local carrier dynamics along composition-graded nanowires, revealing the local variation of composition-dependent carrier mobilities and lifetimes that significantly differ from their uniform composition counterparts. Furthermore, we demonstrate a length-dependent behavior wherein shorter nanowires exhibit enhanced funneling effects, accelerating carrier transport by up to 33%. Our findings provide direct visualization of nanoscale carrier transport while supporting an effective approach for investigating complex carrier interactions in inhomogeneous semiconductor nanostructures, with implications for optimizing next-generation optoelectronic devices.

Yang, Rundi↗
DOE OSTI2024

Ultrafast Production of NiCO and Ni Following 197 nm Photodissociation of Nickel Tetracarbonyl

Herein, we report on the ultrafast photodissociation of nickel tetracarbonyl—a prototypical metal–ligand model system—at 197 nm. Using mid-infrared transient absorption spectroscopy to probe the bound C≡O stretching modes, we find evidence for the picosecond time scale production of highly vibronically excited nickel dicarbonyl and nickel monocarbonyl, in marked contrast with a prior investigation at 193 nm. Further spectral evolution with a 50 ps time constant suggests an additional dissociation step; the absence of any corresponding growth in signal strongly indicates the production of bare Ni, a heretofore unreported product from single-photon excitation of nickel tetracarbonyl. Thus, by probing the deep UV-induced photodynamics of a prototypical metal carbonyl, this Letter adds time-resolved spectroscopic signatures of these dynamics to the sparse literature at high excitation energies.

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

Large Exciton Diffusion Coefficients in Two Dimensional Covalent Organic Frameworks with Different Domain Sizes Revealed by Ultrafast Exciton Dynamics

Large singlet exciton diffusion lengths are a hallmark of high performance in organic-based devices such as photovoltaics, chemical sensors, and photodetectors. In this study, exciton dynamics of a two-dimensional covalent organic framework, 2D COF-S, is investigated using ultrafast spectroscopic techniques. After photoexcitation, the COF-S exciton decays via three pathways: (1) excimer formation (4 +/- 2 ps), (2) excimer relaxation (160 +/- 40 ps), and (3) excimer decay (>3 ns). Excitation fluence-dependent transient absorption studies suggest that COF-5 has a relatively large diffusion coefficient (0.08 cm(2)/s). Furthermore, exciton-exciton annihilation processes are characterized as a function of COF-S crystallite domain size in four different samples, which reveal domain-size-dependent exciton diffusion kinetics. These results reveal that exciton diffusion in COF-S is constrained by its crystalline domain size. These insights indicate the outstanding promise of delocalized excitonic processes available in 2D COFs, which motivate their continued design and implementation into optoelectronic devices.

Flanders, Nathan C.↗