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At least 163 records · Page 9

Light-Induced Charge Separation in Photosystem I from Different Biological Species Characterized by Multifrequency Electron Paramagnetic Resonance Spectroscopy

Photosystem I (PSI) serves as a model system for studying fundamental processes such as electron transfer (ET) and energy conversion, which are not only central to photosynthesis but also have broader implications for bioenergy production and biomimetic device design. In this study, we employed electron paramagnetic resonance (EPR) spectroscopy to investigate key light-induced charge separation steps in PSI isolated from several green algal and cyanobacterial species. Following photoexcitation, rapid sequential ET occurs through either of two quasi-symmetric branches of donor/acceptor cofactors embedded within the protein core, termed the A and B branches. Using high-frequency (130 GHz) time-resolved EPR (TR-EPR) and deuteration techniques to enhance spectral resolution, we observed that at low temperatures prokaryotic PSI exhibits reversible ET in the A branch and irreversible ET in the B branch, while PSI from eukaryotic counterparts displays either reversible ET in both branches or exclusively in the B branch. Furthermore, we observed a notable correlation between low-temperature charge separation to the terminal [4Fe-4S] clusters of PSI, termed F A and F B , as reflected in the measured F A /F B ratio. These findings enhance our understanding of the mechanistic diversity of PSI’s ET across different species and underscore the importance of experimental design in resolving these differences. Though further research is necessary to elucidate the underlying mechanisms and the evolutionary significance of these variations in PSI charge separation, this study sets the stage for future investigations into the complex interplay between protein structure, ET pathways, and the environmental adaptations of photosynthetic organisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical constraints governing the origin of metabolism: the thermodynamic landscape of carbon group transformations under mild aqueous conditions

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies (deltaG) were estimated for four types of reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed (1) that generally when carbon-carbon bond cleavage involves groups from different functional group classes (i.e., carboxylic acids, carbonyl groups, alcohols, and hydrocarbons), the transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) that the energy of carbon-carbon bond transformation is primarily determined by the functional group class of the group that changes oxidation state in the reaction (i.e., the functional group class of the group that donates the shared electron-pair during cleavage, or that accepts the incipient shared electron-pair during synthesis). In contrast, the energy of hydrogen transfer between carbon groups is determined by the functional group class of both the hydrogen-donor group and the hydrogen-acceptor group. From these and other observations we concluded that the chemistry involved in the origin of metabolism (and to a lesser degree modern metabolism) was strongly constrained by (1) the limited redox-based transformation energy of organic substrates that is readily dissipated in a few energetically favorable irreversible reactions; (2) the energy dominance of a few transformation half-reactions that determines whether carbon-carbon bond transformation (cleavage or synthesis) is energetically favorable (deltaG < -3.5 kcal/mol), reversible (deltaG between +/-3.5 kcal/mol), or unfavorable (deltaG > +3.5 kcal/mol); and (3) the dependence of carbon group transformation energy on the functional group class (i.e., oxidation state) of participating groups that in turn is contingent on prior reactions and precursors in the synthetic pathway.

Carbon/chemistry/metabolism↗

Solvent‐Phobic and Ionophilic Carboxylated Polythiophene Layer for Fluoride‐Rich Cathode Electrolyte Interphase

Abstract One focal area of contemporary organic mixed ionic‐electronic conductor (OMIEC) research relates to utilization of dual‐conductive properties to enhance the ion/electron transfer kinetics for energy storage applications. Insight regarding OMIEC response toward the electrolyte anion and solvent used in lithium‐ion batteries (LIBs), however, is limited. Here, for the first time, the solvent‐phobic and ionophilic (SP‐IP) properties of the OMIEC, poly[3‐(potassium‐4‐butanoate)thiophene‐2,5‐diyl] (P3KBT), are revealed through comprehensive evaluation and characterization. The solvent‐phobic characteristics arise from the cooperation of dispersive interaction, polar interaction, and hydrogen‐bonding between P3KBT and electrolyte solvent. The ionophilic nature is driven by electrostatic interactions between P3KBT side chain carboxylate groups and LiPF 6 , and the reversible electrochemical doping/de‐doping of the polythiophene backbone with PF 6 ⁻ . The SP‐IP properties induce formation of a LiF‐ rich , Li 2 CO 3 ‐ limited cathode electrolyte interphase (CEI) layer when a P3KBT coating layer is applied to the active material surface, significantly improving half‐cell life to over 1500 cycles at 2C.

Ren, Haoze [Department of Chemical and Bimolecular↗

Direct coupling of microbore HPLC columns to MS systems

A detailed investigation using electron microscopy was conducted which examined the conditions of materials used in the construction of stable, high performance microbore liquid chromatography (LC) columns. Small details proved to be important. The effects of temperature on the elution of several homologous series used as probe compounds was examined in reverse phase systems. They showed that accessible temperature changes provide roughly half the increase in solvent strength that would be obtained going from a 100% aqueous to a 100% organic mobile phase, which is sufficient to warrant their use in many analyses requiring the use of gradients. Air circulation temperature control systems provide the easiest means of obtaining rapid, wide range changes in column temperature. However, slow heat transfer from the gas leads to thermal nonuniformity in the column and a decrease in resolution as the temperature program progresses.

Mcnair, H. M.↗

Responsive Interfacial Assemblies Based on Charge‐Transfer Interactions

Abstract Charge transfer (CT) interactions have been widely used to construct supramolecular systems, such as functional nanostructures and gels. However, to date, there is no report on the generation of CT complexes at the liquid–liquid interface. Here, by using an electron‐deficient acceptor dissolved in water and an electron‐rich donor dissolved in oil, we present the in situ formation and assembly of CT complex surfactants (CTCSs) at the oil–water interface. With time, CTCSs can assemble into higher‐order nanofilms with exceptional mechanical properties, allowing the stabilization of liquids and offering the possibility to structure liquids into nonequilibrium shapes. Moreover, due to the redox‐responsiveness of the electron‐deficient acceptor, the association and dissociation of CTCSs can be reversibly manipulated in a redox process, leading to the switchable assembly and disassembly of the resultant constructs.

Sun, Shuyi↗

Responsive Interfacial Assemblies Based on Charge‐Transfer Interactions

Abstract Charge transfer (CT) interactions have been widely used to construct supramolecular systems, such as functional nanostructures and gels. However, to date, there is no report on the generation of CT complexes at the liquid–liquid interface. Here, by using an electron‐deficient acceptor dissolved in water and an electron‐rich donor dissolved in oil, we present the in situ formation and assembly of CT complex surfactants (CTCSs) at the oil–water interface. With time, CTCSs can assemble into higher‐order nanofilms with exceptional mechanical properties, allowing the stabilization of liquids and offering the possibility to structure liquids into nonequilibrium shapes. Moreover, due to the redox‐responsiveness of the electron‐deficient acceptor, the association and dissociation of CTCSs can be reversibly manipulated in a redox process, leading to the switchable assembly and disassembly of the resultant constructs.

Sun, Shuyi↗

Engineering Functionalized 2D Metal-Organic Frameworks Nanosheets with Fast Li + Conduction for Advanced Solid Li Batteries

Solid-state batteries can ensure high energy density and safety in lithium metal batteries, while polymer electrolytes are plagued by slow ion kinetics and low selective transport of Li + . Metal-organic frameworks (MOFs) are proposed as emerging fillers for solid-state poly(ethylene oxide)(PEO) electrolytes, however, developing functionalized MOFs and understanding their roles on ion transfer has proven challenging. Herein, combining computational and experimental results, the functional group regulation in MOFs can effectively change surficial charge distribution and limit anion movement is revealed, providing a potential solution to these issues. Specifically, functionalized 2D MOF sheets are designed through molecular engineering to construct high-performance composite electrolytes, where the electron-donating effect of substituents in 2D-MOFs effectively limits the movement of ClO 4 - and promotes mechanical properties and ion migration numbers (0.36 up to 0.64) of PEO. As a result, Li/Li cells with composite electrolyte exhibit superior cyclability for 1000 h at a current density of 0.2 mA cm -2 . Meanwhile, the solid LiFePO 4 /Li battery delivers highly reversible capacities of 148.8 mAh g -1 after 200 cycles. In conclusion, these findings highlight a new approach for anion confinement through the use of functional group electronic effects, leading to enhanced ionic conductivity, and a feasible direction for high-performance solid-state batteries.

25 ENERGY STORAGE↗

Electronic Structure of the Au Nanoparticle-TiO 2 Heterojunction: Influence of Nanoparticle Size, Shape, Oxygen Vacancies, and Temperature

The electronic structure of the gold nanoparticle-titanium dioxide (AuNP-TiO 2 ) heterojunction plays a critical role for charge transfer and recombination dynamics that underpin its photocatalytic function. However, building a representative model to capture the key physics remains a significant challenge. Here, we investigate the influence of the AuNP size and shape, as well as oxygen vacancy (V O ) defects at the anatase-phase TiO 2 (101) surface and the temperature of the heterojunction, on its interfacial electronic properties. Using density functional theory (DFT), we compare the closed-shell Au 20 and open-shell Au 19 clusters interfaced with pristine and V O defect TiO 2 surfaces. We find that the presence of a V O defect transforms pure TiO 2 from a p-type to an n-type semiconductor, reversing the interfacial band bending from downward to upward. For the heterosystem, density of states (DOS) analysis shows that V O minimally affects the open-shell Au 19 -TiO 2 system, but it significantly alters the closed-shell Au 20 -TiO 2 system, converting it from p-type to n-type at the Γ-point at 0 K. Furthermore, ab initio molecular dynamics (AIMD) simulations at 300 K reveal significant thermal fluctuations in AuNP positions relative to the TiO 2 surface. These fluctuations result in dynamic variations in the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in all systems studied: Au 19 NP-Pristine TiO 2 , Au 20 NP-Pristine TiO 2 , Au 19 NP-V O defect TiO 2 , and Au 20 NP-V O defect TiO 2 . Complementary Bader charge analysis performed at both 0 K and finite-temperature AIMD snapshots supports the emergence of an upward band bending and the formation of a Schottky barrier at the V O containing heterojunctions. Notably, we find that at finite temperature, an Au atom can dynamically passivate the V O , leading to a pronounced widening of the HOMO-LUMO gap in the AuNP-V O defect TiO 2 heterojunctions. Our computational findings underscore the pivotal role of the V O defect and thermal effects in modulating interfacial band alignment, electronic states, and HOMO-LUMO gaps, providing insights for designing Au-TiO 2 heterojunctions with tailored electronic properties.

Mora Perez, Carlos [Lawrence Berkeley National Lab↗

In situ XAS study of the local structure of the nano-Li 2 FeSiO 4 /C cathode

Despite the challenges in achieving its full theoretical capacity of reversible extraction of two Li ions, the Li 2 FeSiO 4 (LFS) cathode shows a remarkable cycling stability once its low electronic conductivity is addressed. By studying the local structure around the iron during electrochemical cycling using in situ x-ray absorption spectroscopy (XAS), it is possible to gain insight into the factors which determine the electrochemical properties of this material. In order to practically perform in situ XAS studies, the charge/discharge of LFS was maximized using two approaches: (a) reducing the particle size of LFS samples from micro-scale to nano-scale in order to reduce the diffusion path for intercalating ions; and (b) applying a conductive coating to each nanoparticle to facilitate electron transfer. A family of LFS materials was synthesized and characterized using x-ray diffraction, and scanning electron microscopy with energy dispersive analysis for structural and morphological analysis, as well as cyclic voltammetry and cycling tests for electrochemical performance diagnosis. This material was then characterized by in situ XAS. The results provide insight into the stable electrochemical performance of LFS and suggest new synthetic routes to reaching the theoretical capacity.

25 ENERGY STORAGE↗

Designing Energy-Efficient Quantum Computers Through Prediction and Reduction of Cooling Requirements for Cryogenic Electronics

Quantum computing has been identified as a “wild card” by the International Energy Agency in predicting future global data center energy usage. This is primarily because both uncertainty in the extent to which quantum computing will be adopted, and uncertainty in the power consumption of individual quantum data centers. Unlike the classical counterparts, quantum computers need to be maintained at near absolute zero, requiring energy-intensive cryogenic cooling systems. Therefore, as quantum computers scale up from existing 50 qubit technology demonstrations to the 10,000 to 100,000 qubit systems that will be able to solve complex problems, the energy consumption of both the electronics and the required cooling systems will also increase. To predict this scaling, this work analyzes the energy requirements for both computation and cooling of quantum hardware. We show that the energy requirements for cooling of quantum computers is determined by several computing system parameters, including the number and type of physical qubits, the operating temperature, the packaging efficiency of the system, and the split between circuits operating at cryogenic temperatures and those operating at room temperature. The energy requirements can then be found based on thermal system parameters such as cooling efficiency and cryostat heat transfer. Analysis of these parameters shows that the energy required for cooling is significantly larger than that required for computation, a reversal from energy usage patterns seen in conventional computing. The results and discussions provide a road-map for creating energy efficient quantum computers through the selection of computer architectures and cryogenic system configurations that minimize cooling requirements.

energy efficiency↗

Directly Embedded Ni3S2/Co9S8@S-Doped Carbon Nanofiber Networks as a Free-Standing Anode for Lithium-Ion Batteries

Transition metal sulfides as electrode materials for lithium-ion batteries have attracted significant research attention due to their high theoretical capacity, excellent redox reversibility, and earth abundance. However, this material family still suffers from poor conductivity and experiences huge volume changes. Here, we demonstrate a facile and scalable electrospinning method to prepare Ni3S2 and Co9S8 nanoparticles embedded in sulfur doped carbon nanofiber networks as a free-standing anode material for lithium ion batteries. Similar to literature findings, the coupling of two different metal sulfides indeed synergistically promoted the electrochemical performance. Embedding them within individual carbon nanofibers not only enhances the intrinsic conductivity, but also provides a highly stable structure, which results in excellent battery performance. Furthermore, the individual carbon nanofibers intertwine with each other to form a free-standing 3D nanofiber network which acts as a freeway network for fast electron transfer and the pores between fibers allow easy penetration of the electrolyte, namely easy lithium ion access to active nanoparticles. When directly applied as the anode in lithium ion batteries, the free-standing nanofiber mat bypassed all slurry making steps and showed excellent cycling stability with a high specific capacity of 528 mA h g-1 after 200 cycles at a current density of 300 mA g-1. Good rate capability was also obtained. Additionally, the charge storage process analysis indicated that the pseudocapacitive behavior of the material is attributed to its good performance. This work introduces a facile strategy to simultaneously and in situ generate Co9S8 and Ni3S2 nanoparticles within a S-doped carbon fiber matrix via facile electrospinning followed by a one-step heating procedure. It is demonstrated that the free-standing transition bimetallic sulfide nanofibers prepared are very promising for light and small battery applications.

ADVANCED PROPULSION SYSTEMS,ENERGY STORAGE↗

Employing Long-Range Inductive Effects to Modulate Metal-to-Ligand Charge Transfer Photoluminescence in Homoleptic Cu(I) Complexes

Four Cu(I) bis(phenanthroline) photosensitizers formulated from a new ligand structural motif (Cu1-Cu4) coded according to their 2,9-substituents, were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (1), tetrahydro-2H-pyran-4-yl (2), tetrahydro-2H-thiopyran-4-yl (3), and 4,4-difluorocyclohexyl (4). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited state lifetimes on the microseconds time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in deaerated CH 2 Cl 2 , τ = 2.5 to 4.3 μs. This series of molecules also feature high PL quantum efficiencies (ΦPL = 5.3 to 12% in CH 2 Cl 2 ). Temperature-dependent PL lifetime experiments confirmed that all these molecules exhibit reverse intersystem crossing and display thermally activated delayed PL from a 1 MLCT excited state lying slightly above the 3 MLCT state, 1050 – 1490 cm -1 . Ultrafast and conventional transient absorption measurements confirmed that the PL originates from the MLCT excited state, which remains sterically arrested, preventing an excessive flattening distortion even when dissolved in Lewis basic CH 3 CN. Combined PL and electrochemical data provided evidence that Cu1-Cu4 are highly potent photoreductants (E ox * = -1.73 to -1.62 V vs. Fc +/o in CH 3 CN), whose potentials are altered solely based on which heteroatoms or substituents are resident on the 2,9-appended ring derivatives. It is proposed that long-range electronic inductive effects are responsible for the systematic modulation observed in the PL spectra, excited state lifetimes, as well as the ground state absorption spectra and redox potentials. Cu1-Cu4 quantitatively follow the energy gap law, correlating well with structurally related cuprous phenanthrolines and are also shown to triplet photosensitize the excited states of 9,10-diphenylanthracene with bimolecular rate constants ranging from 1.61 to 2.82 × 10 8 M –1 s –1 . Furthermore, the ability to tailor both photophysical and electrochemical properties using long-range inductive effects imposed by the 2,9-ring platforms advocates new directions for future MLCT chromophore discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast fluctuations of soft X-rays from active regions

A selection of short lived small soft X-ray bursts is studied using data from the Hard X-ray Imaging Spectrometer (HXIS), and the results are compared with the data from the Hard X-Ray Burst Spectrometer (HXRBS) with a view to understanding conditions at the onset of flares. Short-lived events provide an opportunity to study the radiation from the primary energy transfer process without confusion from the slowly-varying thermal X-ray emission which characterizes the decay of a large flare. The fast decay of the soft X-rays, only a few tens of seconds, suggests that they occur in the dense chromosphere. The results indicate that the short events may be signatures of several different phenomena, depending on their characteristics. Some events occur in association with reverse-drift type III bursts and simultaneous flaring elsewhere on the Sun, thus suggesting dumping of particles accelerated at a remote site. Some events have hard X-ray bursts and normal type III bursts associated with them, while others have neither. The latter events place strong constraints on the nonthermal electron population present.

Simnett, G. F.↗

Electrolyte-Dependent, “Microscopically Irreversible” H-Atom Transfer Kinetics of Ce-Based Metal–Organic Framework, Ce-MOF-808

Redox reactions at the interface of metal oxides and protic electrolytes almost always involve protons and electrons in equal amounts. Given the stoichiometry, these proton-coupled electron transfer (PCET) reactions are thermochemically equivalent to net H-atom transfer (HAT) reactions. The correlation between the chemical nature of solid catalysts and HAT kinetics has been employed for decades as the design principle for energy-relevant reactions (e.g., reactions of 2H + /H 2 ). More recently, chemists have experimentally determined that a change in liquid electrolytes that alters the microenvironment at the redox-active sites has an equally profound impact on electrocatalysis involving PCET/HAT. Yet, precise correlations between the chemical nature of electrolytes and the PCET kinetics are, to date, rare in the literature. Herein, we report our findings using the Ce-based metal−organic framework, Ce-MOF-808, as a model system. Each Ce 6 (μ 3 −O) 4 (μ 3 − OH) 4 (OH) 6 (H 2 O) 6 node of this MOF undergoes a 1H + /1e − redox reaction. Using chronoamperometry and the Cottrell analysis, we have determined that the PCET hopping kinetics within the pores of Ce-MOF-808 can change by orders of magnitude by altering the buffer species and the proton activity of the electrolyte. Furthermore, in all buffers, reductive reactions were ∼3−10 times faster in kinetics than the reverse oxidative reaction with the same electrochemical driving force, suggesting that the system, at first glance, violates the principle of microscopic reversibility. Isothermal titration calorimetry (ITC) and computational simulations corroborated that the buffer-node binding thermodynamics are quite distinct, depending on the chemical nature of the buffer and the oxidation state of the node. Together, these results suggest that the substrate and the product during the oxidative vs reductive reaction of Ce-MOF-808 are chemically different species, which explains the apparent ‘microscopic irreversibility.’ Thus, the rational modulation of electrolytes can dramatically enhance PCET kinetics, even though the solid electrodes remain identical. Implications of these findings are contrasted with the electrochemical/electrocatalytic behavior of other redox-active MOFs, heterogeneous catalysts, and enzymatic systems at the solid−liquid interface.

Ce-based MOF↗

Anomalous Hall effects in chiral superconductors

We report theoretical results for the electronic contribution to thermal and electrical transport for chiral superconductors belonging to even or odd-parity E 1 and E 2 representations of the tetragonal and hexagonal point groups. Chiral superconductors exhibit novel properties that depend on the topology of the order parameter and Fermi surface, and—as we highlight—the structure of the impurity potential. An anomalous thermal Hall effect is predicted and shown to be sensitive to the winding number, ν, of the chiral order parameter via Andreev scattering that transfers angular momentum from the chiral condensate to excitations that scatter off the random potential. For heat transport in a chiral superconductor with isotropic impurity scattering, i.e., point-like impurities, a transverse heat current is obtained for ν = ± 1, but vanishes for | ν | > 1. This is not a universal result. For finite-size impurities with radii of order or greater than the Fermi wavelength, R ≥ ℏ / p f, the thermal Hall conductivity is finite for chiral order with | ν | ≥ 2, and determined by a specific Fermi-surface average of the differential cross-section for electron-impurity scattering. Our results also provide quantitative formulae for analyzing and interpreting thermal transport measurements for superconductors predicted to exhibit broken time-reversal and mirror symmetries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cluster observations of quasi-periodic impulsive signatures in the dayside northern lobe: High-latitude flux transfer events?

We report on a series of quasi-periodic reversals in GSM B(sub Z) observed by the four Cluster spacecraft in the northern dayside lobe poleward of the cusp on 23 February 2001. During an interval of about 35 min, multiple reversals (negative to positive) in B(sub Z) of approximately 1-min duration with an approximate 8-min recurrence time were observed. The individual structures do not resemble low-latitude flux transfer events (FTE) [Russell and Elphic, 1979] but the 8-min recurrence frequency suggests that intermittent reconnection may be occurring .Measurements (appropriately lagged) of the solar wind at ACE show that the IMF was southward-oriented with a strong B(sub X) and that a modest dynamic pressure increased as the events started. The multi-point observations afforded by the Cluster spacecraft were used to infer the motion (direction and speed) of the observed magnetic field reversals. The associated currents were also calculated and they are consistent with the spatial confinement of the observed magnetic field reversals. We propose that the observed reversals are due to flux tubes reconnecting with closed field lines on the dayside. Ancillary data from the Cluster Ion Spectrometry (CIS) and Plasma Electron And Current Experiment (PEACE) instruments were used to develop a physical picture of the reversals.

Thompson, S. M.↗

Fusion-Enabled Pluto Orbiter and Lander

The Pluto orbiter mission proposed here is credible and exciting. The benefits to this and all outer-planet and interstellar-probe missions are difficult to overstate. The enabling technology, Direct Fusion Drive, is a unique fusion engine concept based on the Princeton Field-Reversed Configuration (PFRC) fusion reactor under development at the Princeton Plasma Physics Laboratory. The truly game-changing levels of thrust and power in a modestly sized package could integrate with our current launch infrastructure while radically expanding the science capability of these missions. During this Phase I effort, we made great strides in modeling the engine efficiency, thrust, and specific impulse and analyzing feasible trajectories. Based on 2D fluid modeling of the fusion reactors outer stratum, its scrape-off-layer (SOL), we estimate achieving 2.5 to 5 N of thrust for each megawatt of fusion power, reaching a specific impulse, Isp, of about 10,000 s. Supporting this model are particle-in-cell calculations of energy transfer from the fusion products to the SOL electrons. Subsequently, this energy is transferred to the ions as they expand through the magnetic nozzle and beyond. Our point solution for the Pluto mission now delivers 1000 kg of payload to Pluto orbit in 3.75 years using 7.5 N constant thrust. This could potentially be achieved with a single 1 MW engine. The departure spiral from Earth orbit and insertion spiral to Pluto orbit require only a small portion of the total delta-V. Departing from low Earth orbit reduces mission cost while increasing available mission mass. The payload includes a lander, which utilizes a standard green propellant engine for the landing sequence. The lander has about 4 square meters of solar panels mounted on a gimbal that allows it to track the orbiter, which beams 30 to 50 kW of power using a 1080 nm laser. Optical communication provides dramatically high data rates back to Earth. Our mass modeling investigations revealed that if current high-temperature superconductors are utilized at liquid nitrogen temperatures, they drive the mass of the engine, partly because of the shielding required to maintain their critical temperature. Second generation materials are thinner but the superconductor is a very thin layer deposited on a substrate with additional layers of metallic classing. Tremendous research is being performed on a variety of these superconducting materials, and new irradiation data is now available. This raises the possibility of operating nearfuture high-temperature superconductors at a moderately low temperature to dramatically reduce the amount of shielding required. At the same time, a first generation space engine may require low-temperature superconductors, which are higher TRL and have been designed for space coils before (AMS-02 experiment for the ISS). We performed detailed analysis of the startup system and thermal conversion system components. The ideal working fluid was determined to be a blend of Helium and Xenon. No significant problems were identified with these subsystems. For the RF system, we conceived of a new, more efficient design using state-of-the-art switch amplifiers, which have the potential for 100% efficiency. This report presents details of our engine and trajectory analyses, mass modeling efforts, and updated vehicle designs.

temperature↗