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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Quantum-enhanced photoprotection in neuroprotein architectures emerges from collective light-matter interactions

Background Superradiance is the phenomenon of many identical quantum systems absorbing and/or emitting photons collectively at a higher rate than any one system can individually. This phenomenon has been studied analytically in idealized distributions of electronic two-level systems (TLSs), each with a ground and excited state, as well as numerically in realistic photosynthetic nanotubes and cytoskeletal architectures. Methods Superradiant effects are studied here in idealized toy model systems and realistic biological mega-networks of tryptophan (Trp) molecules, which are strongly fluorescent amino acids found in many proteins. Each Trp molecule acts as a chromophore absorbing in the ultraviolet spectrum and can be treated approximately as a TLS, with its 1 L a excited singlet state; thus, organized Trp networks can exhibit superradiance. Such networks are found, for example, in microtubules, actin filaments, and amyloid fibrils. Microtubules and actin filaments are spiral-cylindrical protein polymers that play significant biological roles as primary constituents of the eukaryotic cytoskeleton, while amyloid fibrils have been targeted in a variety of neurodegenerative diseases. We treat these proteinaceous Trp networks as open quantum systems, using a non-Hermitian Hamiltonian to describe interactions of the chromophore network with the electromagnetic field. We numerically diagonalize the Hamiltonian to obtain its complex eigenvalues, where the real part is the energy and the imaginary part is its associated enhancement rate. We also consider multiple realizations of increasing static disorder in either the site energies or the decay rates. Results We obtained the energies and enhancement rates for realistic microtubules, actin filament bundles, and amyloid fibrils of differing lengths, and we use these values to calculate the quantum yield, which is the ratio of the number of photons emitted to the number of photons absorbed. We find that all three of these structures exhibit highly superradiant states near the low-energy portion of the spectrum, which enhances the magnitude and robustness of the quantum yield to static disorder and thermal noise. Conclusion The high quantum yield and stable superradiant states in these biological architectures may play a photoprotective rolein vivo, downconverting energetic ultraviolet photons—absorbed from those emitted by reactive free radical species—to longer, safer wavelengths and thereby mitigating biochemical stress and photophysical damage. Contrary to conventional assumptions that quantum effects cannot survive in large biosystems at high temperatures, our results suggest that macropolymeric collectives of TLSs in microtubules, actin filaments, and amyloid fibrils exhibit increasingly observable and robust effects with increasing length, up to the micron scale, due to quantum coherent interactions in the single-photon limit. Superradiant enhancement and high quantum yield exhibited in neuroprotein polymers could thus play a crucial role in information processing in the brain, the development of neurodegenerative diseases such as Alzheimer’s and related dementias, and a wide array of other pathologies characterized by anomalous protein aggregates.

Physics↗
DOE OSTI2022

Phytochrome-Dependent Regulation of ZFP6 and ZFPH Impacts Photomorphogenesis in Arabidopsis thaliana

Phytochromes (phy) are key regulators of photomorphogenesis in plants. Among the different phys characterized in higher plants (i.e., phyA to phyE), phyA and phyB primarily regulate phenotypic responses in plants under far-red (FR) and red (R) conditions, respectively. Recent findings suggest that some zinc finger proteins (ZFPs) are involved in plant light-modulated morphogenesis. However, the interaction(s) between phyA, phyB and ZFP homologs potentially involved in photomorphogenesis, as well as their phenotypic and molecular effects in Arabidopsis seedlings exposed to R and FR light remain to be elucidated fully. Prior analyses with phytochrome chromophore deficient lines indicated that ZFP6 expression is misregulated compared to levels in Col-0 wild type (WT). Here, we used plants with phytochrome chromophore or apoprotein (specifically phyA and phyB) deficiencies, lines with mutations in ZFP6 and ZFP6 HOMOLOG ( ZFPH ) genes, and plants overexpressing ZFP6 to examine regulatory interactions between phytochromes, ZFP6, and ZFPH. Our results indicate that phytochromes are required for downregulation of ZFP6 and ZFPH and suggest a role for light-regulated control of ZFP levels in phytochrome-dependent photomorphogenesis. Conversely, PHYB is downregulated in zfp6 mutants under R light. Analyses of a zfp6zfph double mutant confirmed disruption in photomorphogenic phenotypes, including the regulation of hypocotyl elongation in seedlings grown under FR light. In addition, PIF3 and PIF4 levels are transcriptionally regulated by ZFP6 and ZFPH in a gibberellic acid-dependent manner. ZFP6 overexpression resulted in opposite phenotypic responses to those observed in the zfp6 and zfph mutants grown in FR and R light, as well as a reduction in the rosette size of mature ZFP6 OX plants relative to WT under white light. Based on these observations, we provide insight into how phy and ZFPs interact to regulate specific aspects of light-dependent processes in Arabidopsis.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Photoluminescence Induced in Mineral Oil by Ionizing Radiation

We have studied photoluminescence (PL) properties of vacuum pump mineral oil as a function of the type and intensity of ionizing radiation exposure. The mineral oil has a simple aliphatic structure, which possesses no chromophore in the traditional sense. Unexpected PL in the mineral oil has characteristic features such as variation of the emission peak wavelength depending on the excitation wavelength and intensity dramatically increasing with radiation dose. The observed behavior can be understood in the framework of a previously suggested model introducing aggregation-induced PL and the formation of conjugated clusters comprising nontraditional chromophores. Our findings can be used for the development of optical sensors for real-time monitoring of oil utilized in vacuum pumps in nuclear fusion reactors.

Bliznyuk, Valery N.↗
DOE OSTI2020

The Effect of Periodic Spatial Perturbations on the Emission Rates of Quantum Dots near Graphene Platforms

The quenching of fluorescence (FL) at the vicinity of conductive surfaces and, in particular, near a 2-D graphene layer has become an important biochemical sensing tool. The quenching is attributed to fast non-radiative energy transfer between a chromophore (here, a Quantum Dot, QD) and the lossy graphene layer. Increased emission rate is also observed when the QD is coupled to a resonator. Here, we combine the two effects in order to control the emission lifetime of the QD. In our case, the resonator was defined by an array of nano-holes in the oxide substrate underneath a graphene surface guide. At resonance, the surface mode of the emitted radiation is concentrated at the nano-holes. Thus, the radiation of QD at or near the holes is spatially correlated through the hole-array’s symmetry. We demonstrated an emission rate change by more than 50% as the sample was azimuthally rotated with respect to the polarization of the excitation laser. In addition to an electrical control, such control over the emission lifetime could be used to control Resonance Energy Transfer (RET) between two chromophores.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Optical Spin Polarization of a Narrow-Linewidth Electron-Spin Qubit in a Chromophore/Stable-Radical System

Photoexcited organic chromophores appended to stable radicals can serve as qubit and/or qudit candidates for quantum information applications. 1,6,7,12-Tetra-(4-tert-butylphenoxy)-perylene-3,4 : 9,10-bis(dicarboximide) (tpPDI) linked to a partially deuterated α,γ-bisdiphenylene-β-phenylallyl radical (BDPA-d 16 ) was synthesized and characterized by time-resolved optical and electron paramagnetic resonance (EPR) spectroscopies. Photoexcitation of tpPDI-BDPA-d 16 results in ultrafast radical-enhanced intersystem crossing to produce a quartet state (Q) followed by formation of a spin-polarized doublet ground state (D 0 ). Pulse-EPR experiments confirmed the spin multiplicity of Q and yielded coherence times of T m =2.1±0.1 μs and 2.8±0.2 μs for Q and D 0 , respectively. BDPA-d 16 eliminates the dominant 1 H hyperfine couplings, resulting in a single narrow line for both the Q and D 0 states, which enhances the spectral resolution needed for good qubit addressability.

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

A Computational Framework for Simulations of Dissipative Nonadiabatic Dynamics on Hybrid Oscillator-Qubit Quantum Devices

Here, we introduce a computational framework for simulating nonadiabatic vibronic dynamics on circuit quantum electrodynamics (cQED) platforms. Our approach leverages hybrid oscillator-qubit quantum hardware with midcircuit measurements and resets, enabling the incorporation of environmental effects such as dissipation and dephasing. To demonstrate its capabilities, we simulate energy transfer dynamics in a triad model of photosynthetic chromophores inspired by natural antenna systems. We specifically investigate the role of dissipation during the relaxation dynamics following photoexcitation, where electronic transitions are coupled to the evolution of quantum vibrational modes. Our results indicate that hybrid oscillator-qubit devices, operating with noise levels below the intrinsic dissipation rates of typical molecular antenna systems, can achieve the simulation fidelity required for practical computations on near-term and early fault-tolerant quantum computing platforms.

Hamiltonians↗
DOE OSTI2023

Red-Colored Circularly Polarized Luminescence from a Benzo-Fused BODIPY-BINOL Complex

Red emission with sharp bandwidth and high quantum yield are desired characteristics for organic chromophores in optoelectronic, spintronic, and biomedical applications. Here, we observe circularly polarized luminescence (CPL) with these characteristics from a benzo-fused BODIPY-BINOL complex (1). Using time-resolved optical spectroscopy, electrochemistry, and density functional theory calculations, we showed that the emissive excited state of 1 does not have a charge-transfer character, unlike the regular BODIPY counterpart (2). In conclusion, the rigidity and the lack of charge-transfer character make this class of molecules an appealing platform for CPL-active molecules in the red spectral region with ample room for improvement in the dissymmetry factor and brightness.

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

Dissipation Pathways in a Photosynthetic Complex

Determining how energy flows within and between molecules is crucial for understanding chemical reactions, material properties, and even vital processes such as photosynthesis. While the general principles of energy transfer are well established, elucidating the specific molecular pathways by which energy is funneled remains challenging, as it requires tracking energy flow in complex molecular environments. Here, we demonstrate how photon excitation energy is partially dissipated in the light-harvesting Fenna–Matthews–Olson (FMO) complex, mediating the excitation energy transfer from light-harvesting chlorosomes to the photosynthetic reaction center in green sulfur bacteria. Specifically, we isolate the contribution of the protein and specific vibrational modes of the pigment molecules to the energy dynamics. For this, we introduce an efficient computational implementation of a recently proposed theory of dissipation pathways for open quantum systems, based on second-order perturbation theory in the electronic couplings. Using it and a state-of-the-art FMO model with highly structured and chromophore-specific spectral densities, we demonstrate that energy dissipation is dominated by low-frequency modes (<800 cm –1 ) as their energy range is near-resonance with the energy gaps between electronic states of the pigments. We identify the most important modes for dissipation to be in-plane breathing modes (∼200 cm –1 ) of the bacteriochlorophylls in the complex. Conversely, far-detuned intramolecular vibrations with higher frequencies (>800 cm –1 ) play no role in dissipation. Interestingly, the FMO complex first needs to borrow energy from the environment to release excess photonic energy, indicating that the energy exchange between the system and thermal environment is not strictly unidirectional in time but involves a transient thermally activated step. Beyond their fundamental value, these insights can guide the development of artificial light-harvesting devices and, more broadly, engineer environments for chemical and quantum control tasks.

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

Regulation of Absorption and Emission in a Protein/Fluorophore Complex

Human cellular retinol binding protein II (hCRBPII) was used as a protein engineering platform to rationally regulate absorptive and emissive properties of a covalently bound fluorogenic dye. We demonstrate the binding of a thio-dapoxyl analog via formation of a protonated imine between an active site lysine residue and the chromophore’s aldehyde. Rational manipulation of the electrostatics of the binding pocket results in a 204 nm shift in absorption and a 131 nm shift in emission. The protein is readily expressed in mammalian systems and binds with exogenously delivered fluorophore as demonstrated by live-cell imaging experiments.

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

Role of Spin–Orbit Coupling in Long Range Energy Transfer in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are emerging as a promising platform for solar energy conversion applications. Their potential utilization as efficient chromophores in artificial photosynthesis is closely related to the understanding of light-harvesting and energy transfer processes that occur within these molecular scaffolds. Herein, we present the photophysical investigation of Ru(II), Ir(III), and Os(II) polypyridyl complexes incorporated into the backbone of UiO-67. In this work, we systematically study the effect of spin–orbit coupling on dipole–dipole energy transfer in MOFs using steady-state and time-resolved spectroscopic techniques. The results of our work indicate successful triplet-to-singlet energy transfer and a sizable increase in the transfer kinetics and critical distance, as direct consequences of strong spin–orbit couplings. Remarkably, the reported R 0 value for OsDCBPY (R 0 = 88 ± 10 Å) represents one of the largest Förster distances observed in an MOF. Collectively, this work contributes to the general knowledge of energy transfer in materials and provides groundwork for efficient utilization in artificial photosynthetic assemblies.

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

Photocatalytic Aqueous CO 2 Reduction to CO and CH 4 Sensitized by Ullazine Supramolecular Polymers

There has been rapid progress on the chemistry of supramolecular scaffolds that harness sunlight for aqueous photocatalytic production of hydrogen. However, great efforts are still needed to develop similar photosynthetic systems for the great challenge of CO 2 reduction especially if they avoid the use of nonabundant metals. This work investigates the synthesis of supramolecular polymers capable of sensitizing catalysts that require more negative potentials than proton reduction. The monomers are chromophore amphiphiles based on a diareno-fused ullazine core that undergo supramolecular polymerization in water to create entangled nanoscale fibers. Under 450 nm visible light these fibers sensitize a dinuclear cobalt catalyst for CO 2 photoreduction to generate carbon monoxide and methane using a sacrificial electron donor. The supramolecular photocatalytic system can generate amounts of CH 4 comparable to those obtained with a precious metal-based [Ru(phen) 3 ](PF 6 ) 2 sensitizer and, in contrast to Ru-based catalysts, retains photocatalytic activity in all aqueous media over 6 days. Furthermore, the present study demonstrates the potential of tailored supramolecular polymers as renewable energy and sustainability materials.

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

Single-Photon-Induced Electron Spin Polarization of Two Exchange-Coupled Stable Radicals

Transient electron paramagnetic resonance spectroscopy has been used to probe photoinduced electron spin polarization of a stable exchange-coupled organic biradical in a Pt(II) complex comprising 4,4'-di-tert-butyl-2,2'-bipyridine (bpy) and 3,6-bis(ethynyl-para-phenyl-nitronyl nitroxide)-o-catecholate (CAT(o-C$\equiv$C-Ph-NN) 2 ). Photoexcitation results in four unpaired spins in excited states of this complex, with spins being localized on each of the two radicals, CAT •+ and bpy •– . The four spins are all exchange-coupled in these excited states, and an off-diagonal matrix element in the CAT •+ -NN exchange allows for exchange-enhanced intersystem crossing to the 3 T 1a state, which possesses (bpy •– )Pt(CAT •+ ) chromophoric triplet character. Further, fast mixing between this 3 T 1a state and other thermally accessible excited LL'CT state(s) followed by fast relaxation provides spin polarization of the exchange-coupled NN radicals in the 3 S 0 ground state of the complex. Our results demonstrate that well-defined quantum states of a ground-state biradical can be initialized with single-photon excitation and have the potential for further spin manipulation directed toward quantum information science applications.

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

Unraveling the mechanism of tip-enhanced molecular energy transfer

Electronic Energy Transfer (EET) between chromophores is fundamental in many natural light-harvesting complexes, serving as a critical step for solar energy funneling in photosynthetic plants and bacteria. The complicated role of the environment in mediating this process in natural architectures has been addressed by recent scanning tunneling microscope experiments involving EET between two molecules supported on a solid substrate. These measurements demonstrated that EET in such conditions has peculiar features, such as a steep dependence on the donor-acceptor distance, reminiscent of a short-range mechanism more than of a Förster-like process. By using state of the art hybrid ab initio/electromagnetic modeling, here we provide a comprehensive theoretical analysis of tip-enhanced EET. In particular, we show that this process can be understood as a complex interplay of electromagnetic-based molecular plasmonic processes, whose result may effectively mimic short range effects. Therefore, the established identification of an exponential decay with Dexter-like effects does not hold for tip-enhanced EET, and accurate electromagnetic modeling is needed to identify the EET mechanism.

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

Enhancement of Photovoltaic Current through Dark States in Donor–Acceptor Pairs of Tungsten–Based Transition Metal Di–Chalcogenides

As several photovoltaic materials experimentally approach the Shockley– Queisser limit, there has been a growing interest in unconventional materials and approaches with the potential to cross this efficiency barrier. One such candidate is dark state protection induced by the dipole–dipole interaction between molecular excited states. This phenomenon has been shown to significantly reduce carrier recombination rate and enhance photon-to-current conversion, in elementary models consisting of few interacting chromophore centers. Atomically thin 2D transition metal di-chalcogenides (TMDCs) have shown great potential for use as ultrathin photovoltaic materials in solar cells due to their favorable photon absorption and electronic transport properties. TMDC alloys exhibit tunable direct bandgaps and significant dipole moments. In this work, the dark state protection mechanism has been introduced to a TMDC based photovoltaic system with pure tungsten diselenide (WSe 2 ) as the acceptor material and the TMDC alloy tungsten sulfo-selenide (WSeS) as the donor material. Furthermore, our numerical model demonstrates the first application of the dark state protection mechanism to a photovoltaic material with a photon current enhancement of up to 35% and an ideal photon-to-current efficiency exceeding the Shockley–Queisser limit.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Identifying the Signatures of Intermolecular Interactions in Blends of PM6 with Y6 and N4 Using Absorption Spectroscopy

Abstract In organic solar cells, the resulting device efficiency depends strongly on the local morphology and intermolecular interactions of the blend film. Optical spectroscopy was used to identify the spectral signatures of interacting chromophores in blend films of the donor polymer PM6 with two state‐of‐the‐art nonfullerene acceptors, Y6 and N4, which differ merely in the branching point of the side chain. From temperature‐dependent absorption and luminescence spectroscopy in solution, it is inferred that both acceptor materials form two types of aggregates that differ in their interaction energy. Y6 forms an aggregate with a predominant J‐type character in solution, while for N4 molecules the interaction is predominantly in a H‐like manner in solution and freshly spin‐cast film, yet the molecules reorient with respect to each other with time or thermal annealing to adopt a more J‐type interaction. The different aggregation behavior of the acceptor materials is also reflected in the blend films and accounts for the different solar cell efficiencies reported with the two blends.

Kroh, Daniel↗
DOE OSTI2022

Direct Exciton Harvesting from a Bound Triplet Pair

Abstract Singlet fission is commonly defined as the generation of two triplet excitons from a single absorbed photon. However, ambiguities within this definition arise due to the complexity of the various double triplet states that exist in SF chromophores and the corresponding interconversion processes. To clarify this process, singlet fission is frequently depicted as sequential two‐step conversion in which a singlet exciton decays into a bound triplet‐pair biexciton state that dissociates into two “free” triplet excitons. However, this model discounts the potential for direct harvesting from the coupled biexciton state. Here, it is demonstrated that individual triplet excitons can be extracted directly from a bound triplet pair. It is demonstrated that due to the requirement for geminate triplet–triplet annihilation in intramolecular singlet fission compounds, unique spectral and kinetic signatures can be used to quantify triplet‐pair harvesting yields. An internal quantum efficiency for triplet exciton transfer from the triplet pair of >50%, limited only by the solubility of the compounds is achieved. The harvesting process is not dependent on the net multiplicity of the triplet‐pair state, suggesting that an explicit, independent dissociation step is not a requirement for using triplet pairs to do chemical or electrical work.

Chemistry↗
DOE OSTI2024

Free-Charge Carrier Generation in Homojunction Non-Polymeric Organic Semiconductor Films - The Role of the Optical Frequency Dielectric Constant

Engineering the dielectric constant (..epsilon..) to lower the exciton binding energy of the light-absorbing semiconductor can improve organic photovoltaic (OPV) device performance. Here, a series of materials are reported with 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) acceptor end groups and a central glycolated bis(4H-cyclopenta[2,1-b:3,4-b']dithiophene) unit with large low-frequency (..epsilon..lf = 7.4-7.9 at 0.1-0.2 MHz) and optical-frequency (..epsilon..opt up to 6.6 at 2 x 1014 Hz) dielectric constants. The INCN end groups differed in whether they were protonated, chlorinated, or fluorinated, with the latter having the highest ..epsilon..opt. An ..epsilon..opt of 6.6 is predicted to lead to a low exciton binding energy of ~0.04 eV. Time-resolved microwave conductivity measurements showed a temperature-dependent yield-mobility product, with it increasing linearly from 340 K. The onset temperature was near that required to overcome the calculated exciton binding energy and indicates increased free charge generation in a homojunction film. Room temperature transient absorption spectroscopy revealed that photoexcitation rapidly converted to a lower energy state that was consistent with the formation of polarons or a charge transfer state. This work provides experimental evidence of the importance of ..epsilon..opt for the generation of free charges, and a strategy for development of efficient single chromophore homojunction OPV devices.

charge generation↗