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At least 1,747 records · Page 97

Strong electron-phonon coupling driven pseudogap modulation and density-wave fluctuations in a correlated polar metal

Abstract There is tremendous interest in employing collective excitations of the lattice, spin, charge, and orbitals to tune strongly correlated electronic phenomena. We report such an effect in a ruthenate, Ca 3 Ru 2 O 7 , where two phonons with strong electron-phonon coupling modulate the electronic pseudogap as well as mediate charge and spin density wave fluctuations. Combining temperature-dependent Raman spectroscopy with density functional theory reveals two phonons, B 2 P and B 2 M , that are strongly coupled to electrons and whose scattering intensities respectively dominate in the pseudogap versus the metallic phases. The B 2 P squeezes the octahedra along the out of plane c -axis, while the B 2 M elongates it, thus modulating the Ru 4d orbital splitting and the bandwidth of the in-plane electron hopping; Thus, B 2 P opens the pseudogap, while B 2 M closes it. Moreover, the B 2 phonons mediate incoherent charge and spin density wave fluctuations, as evidenced by changes in the background electronic Raman scattering that exhibit unique symmetry signatures. The polar order breaks inversion symmetry, enabling infrared activity of these phonons, paving the way for coherent light-driven control of electronic transport.

36 MATERIALS SCIENCE↗

Design and performance of a magnetic bottle electron spectrometer for high-energy photoelectron spectroscopy

We describe the design and performance of a magnetic bottle electron spectrometer (MBES) for high-energy electron spectroscopy. Our design features a 2 m long electron drift tube and electrostatic retardation lens, achieving sub-electronvolt (eV) electron kinetic energy resolution for high energy (several hundred eV) electrons with a close to 4π collection solid angle. A segmented anode electron detector enables the simultaneous collection of photoelectron spectra in high resolution and high collection efficiency modes. This versatile instrument is installed at the time-resolved molecular and optical sciences instrument at the Linac Coherent Light Source x-ray free-electron laser (XFEL). In this paper, we demonstrate its high resolution, collection efficiency, and spatial selectivity in measurements where it is coupled to an XFEL source. These combined characteristics are designed to enable high-resolution time-resolved measurements using x-ray photoelectron, absorption, and Auger–Meitner spectroscopy. We also describe the pervasive artifact in MBES time-of-flight spectra that arises from a periodic modulation in electron collection efficiency and present a robust analysis procedure for its removal.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Selective acoustic control of photon-mediated qubit-qubit interactions

Quantum technologies such as quantum sensing, quantum imaging, quantum communications, and quantum computing rely on the ability to actively manipulate the quantum state of light and matter. Quantum emitters, such as color centers trapped in solids, are a useful platform for the realization of elementary building blocks (qubits) of quantum information systems. In particular, the modular nature of such solid-state devices opens up the possibility to connect them into quantum networks and create nonclassical states of light shared among many qubits. The function of a quantum network relies on efficient and controllable interactions among individual qubits. In this context, we present a scheme where optically active qubits of differing excitation energies are mutually coupled via a dispersive interaction with a shared mode of an optical cavity. This generally off-resonant interaction is prohibitive of direct exchange of information among the qubits. However, we propose a scheme in which by acoustically modulating the qubit excitation energies it is, in fact, possible to tune to resonance a preselected pair of qubits and thus open a communication channel between them. This method potentially enables fast (approximately nanoseconds) and parallelizable on-demand control of a large number of physical qubits. In this work, we develop an analytical and a numerical theoretical model demonstrating this principle and suggest feasible experimental scenarios to test the theoretical predictions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Simultaneous amplification of terahertz difference frequencies by an injection-seeded semiconductor laser amplifier at 850 nm

Two-frequency operation of an 850 nm semiconductor optical amplifier was achieved by simultaneously injection seeding it with two diode lasers. The two frequencies could be independently amplified without strong interference when they were separated by more than 10 GHz, and the spectral purity was preserved by the amplification process. At frequency differences below 10 GHz, unbalanced two-frequency output was observed, which can be explained by a two-mode interaction driven by the refractive index modulation at the beat frequency. The laser system is suitable for the difference-frequency generation of coherent terahertz radiation in ultra-fast photoconductors or nonlinear optical media.

NASA Discipline Exobiology↗

Optical Communications from Planetary Distances

Future planetary campaigns, including human missions, will require data rates difficult to realize by microwave links. Optical channels not only provide an abundance of bandwidth, they also allow for significant size, weight, and power reduction. Moreover, optical-based tracking may enhance spacecraft navigation with respect to microwave-based tracking. With all its advantages, optical communications from deep space is not without its challenges. Due to the extreme distance between the two ends of the link, specialized technologies are needed to enable communications in the deep space environment. Although some of the relevant technologies have been developed in the last decade, they remain to be validated in an appropriate domain. The required assets include efficient pulsed laser sources, modulators, transmitters, receivers, detectors, channel encoders, precise beam pointing technologies for the flight transceiver and large apertures for the ground receiver. Clearly, space qualification is required for the systems that are installed on a deep space probe. Another challenge is atmospheric effects on the optical beam. Typical candidate locations on the ground have a cloud-free line of sight only on the order of 60-70% of the time. Furthermore, atmospheric losses and background light can be problematic even during cloud-free periods. Lastly, operational methodologies are needed for efficient and cost effective management of optical links. For more than a decade, the National Aeronautics and Space Administration (NASA) has invested in relevant technologies and procedures to enable deep space optical communications capable of providing robust links with rates in the order of 1 Gb/s from Mars distance. A recent publication indicates that potential exists for 30-dB improvement in performance through technology development with respect to the state-of-the-art in the early years of this decade. The goal is to fulfill the deep space community needs from about 2020 to the foreseeable future. It is envisioned that, at least initially, optical links will be complemented by microwave assets for added robustness, especially for human missions. However, it is expected that as optical techniques mature, laser communications may be operated without conventional radio frequency links. The purpose of this paper is to briefly review the state-of-the-art in deep space laser communications and its challenges and discuss NASA-supported technology development efforts and plans for deep space optical communications at JPL.

Laser Communications↗

The Ultracompact Nature of the Black Hole Candidate X-Ray Binary 47 Tuc X9

47 Tuc X9 is a low-mass X-ray binary (LMXB) in the globular cluster 47 Tucanae, and was previously thought to be a cataclysmic variable. However, Miller-Jones et al. recently identified a radio counterpart to X9 (inferring a radio X-ray luminosity ratio consistent with black hole LMXBs), and suggested that the donor star might be a white dwarf. We report simultaneous observations of X9 performed by Chandra, NuSTAR and Australia Telescope Compact Array. We find a clear 28.18+/- 0.02-min periodic modulation in the Chandra data, which we identify as the orbital period, confirming this system as an ultracompact X-ray binary. Our X-ray spectral fitting provides evidence for photoionized gas having a high oxygen abundance in this system, which indicates a CO white dwarf donor. We also identify reflection features in the hard X-ray spectrum, making X9 the faintest LMXB to show X-ray reflection. We detect an approx. 6.8-d modulation in the X-ray brightness by a factor of 10, in archival Chandra, Swift and ROSAT data. The simultaneous radio X-ray flux ratio is consistent with either a black hole primary or a neutron star primary, if the neutron star is a transitional millisecond pulsar. Considering the measured orbital period (with other evidence of a white dwarf donor), and the lack of transitional millisecond pulsar features in the X-ray light curve, we suggest that this could be the first ultracompact black hole X-ray binary identified in our Galaxy.

accretion↗

Ferroelectric Domain Wall Engineering Enables Thermal Modulation in PMN–PT Single Crystals

Acting like thermal resistances, ferroelectric domain walls can be manipulated to realize dynamic modulation of thermal conductivity ( k ), which is essential for developing novel phononic circuits. Despite the interest, little attention has been paid to achieving room-temperature thermal modulation in bulk materials due to challenges in obtaining a high thermal conductivity switching ratio ( k high / k low ), particularly in commercially viable materials. Here, room-temperature thermal modulation in 2.5 mm-thick Pb(Mg 1/3 Nb 2/3 )O 3 – x PbTiO 3 (PMN– x PT) single crystals is demonstrated. With the use of advanced poling conditions, assisted by the systematic study on composition and orientation dependence of PMN– x PT, a range of thermal conductivity switching ratios with a maximum of ≈1.27 is observed. Further, simultaneous measurements of piezoelectric coefficient (d 33 ) to characterize the poling state, domain wall density using polarized light microscopy (PLM), and birefringence change using quantitative PLM reveal that compared to the unpoled state, the domain wall density at intermediate poling states (0< d 33 33,max ) is lower due to the enlargement in domain size. At optimized poling conditions (d 33,max ), the domain sizes show increased inhomogeneity that leads to enhancement in the domain wall density. This work highlights the potential of commercially available PMN– x PT single crystals among other relaxor-ferroelectrics for achieving temperature control in solid-state devices.

36 MATERIALS SCIENCE↗

Editorial special issue: Advancing foundational sun-induced chlorophyll fluorescence science

The first research on the possibilities offered by chlorophyll-a fluorescence to track the daily course of CO 2 assimilation by leaves dates back to the last century (Kautsky and Hirsch, 1931). In the second half of the XXth Century, the development of the field of active fluorescence, which relies mainly on the pulse amplitude modulation (PAM) fluorimetry technique, allowed the unraveling of the relationship between the yield of chlorophyll-a fluorescence and photochemistry (linear electron transport), which is modulated by a third process known as non-photochemical quenching (Genty et al., 1989). Since then, active fluorescence has been regularly used in ecophysiology, forestry, and crop sciences to understand the plant response to stress (Schreiber, 2004). Since the beginning of the 2000s, the development of portable field spectrometers allows for measuring passive sun-induced fluorescence (SIF) at strong solar or telluric absorption features, which do not rely on the use of artificial excitation light (e.g., Meroni and Colombo, 2006; Meroni et al., 2009; Perez-Priego et al., 2005). Since then, the field has rapidly evolved, and now fluorescence is measurable with automated field spectrometers in the field (Grossmann et al., 2018; Gu et al., 2019b; Rossini et al., 2010), airborne platforms (Rascher et al., 2015; Zarco-Tejada et al., 2000), and satellites (Guanter et al., 2012; Sun et al., 2018). These advances offer the potential to couple ecosystem-scale measurements of CO 2 fluxes and SIF to probe new aspects related to ecosystem structural impacts on SIF andphotosynthesis processes at different time-scales and on different ecosystems (e.g., Damm et al., 2010; Magney et al., 2019; Porcar-Castell et al., 2021). While SIF has been proven as a good proxy of gross primary productivity (GPP), mainly across large spatial and temporal gradients, a series of studies showed that different factors could confound this relationship, namely different canopy structures (e.g., Dechant et al., 2020; Migliavacca et al., 2017), stress conditions (e.g., Martini et al., 2022; Wieneke et al., 2018; Wohlfahrt et al., 2018), nutritional conditions (Cendrero-Mateo et al., 2015; Martini et al., 2019), species-specific differences (e.g., Van Wittenberghe et al., 2013) and light regimes (e.g., Liu and Liu, 2018). At the same time, the modeling of SIF developed rapidly (Gu et al., 2019a; Han et al., 2022; Han et al., 2021; van der Tol et al., 2014; van der Tol et al., 2009) and with an increasing degree of realism, offering the possibility to retrieve important vegetation parameters from remote sensing (Pacheco-Labrador et al., 2019; Verrelst et al., 2015; Verrelst et al., 2016; Zhang et al., 2014). Excellent and comprehensive reviews of the field are by (Mohammed et al., 2019; Porcar-Castell et al., 2021; Porcar-Castell et al., 2014; Sun et al., 2023a; Sun et al., 2023b). Despite the exponential increase in the number of publications in the field, significant progress is still needed. Here, this special issue aims to report foundational SIF science, including theoretical modeling and measurement-based research that is urgently needed to unleash the full potential of SIF for physiological and ecological applications at scales spanning from leaf to globe. The 14 articles collected in this special issue reported on the following specific aspects: first, technical capabilities enabling spectrally resolved SIF observations and their inter-comparability in space and time; second, theoretical developments in SIF-photosynthesis relationships to correctly interpret the signal and extract mechanistic information on vegetation structure and function; third, evaluation of the potential of SIF to track process beyond photosynthesis, such as transpiration; fourth, large scale-applications of SIF observations; and finally, upscaling fluorescence from leaf to canopy scales.

54 ENVIRONMENTAL SCIENCES↗

Transcriptomic Analysis of the CAM Species Kalanchoë fedtschenkoi Under Low- and High-Temperature Regimes

Temperature stress is one of the major limiting environmental factors that negatively impact global crop yields. Kalanchoë fedtschenkoi is an obligate crassulacean acid metabolism (CAM) plant species, exhibiting much higher water-use efficiency and tolerance to drought and heat stresses than C 3 or C 4 plant species. Previous studies on gene expression responses to low- or high-temperature stress have been focused on C 3 and C 4 plants. There is a lack of information about the regulation of gene expression by low and high temperatures in CAM plants. To address this knowledge gap, we performed transcriptome sequencing (RNA-Seq) of leaf and root tissues of K. fedtschenkoi under cold (8 °C), normal (25 °C), and heat (37 °C) conditions at dawn (i.e., 2 h before the light period) and dusk (i.e., 2 h before the dark period). Our analysis revealed differentially expressed genes (DEGs) under cold or heat treatment in comparison to normal conditions in leaf or root tissue at each of the two time points. In particular, DEGs exhibiting either the same or opposite direction of expression change (either up-regulated or down-regulated) under cold and heat treatments were identified. In addition, we analyzed gene co-expression modules regulated by cold or heat treatment, and we performed in-depth analyses of expression regulation by temperature stresses for selected gene categories, including CAM-related genes, genes encoding heat shock factors and heat shock proteins, circadian rhythm genes, and stomatal movement genes. Our study highlights both the common and distinct molecular strategies employed by CAM and C 3 /C 4 plants in adapting to extreme temperatures, providing new insights into the molecular mechanisms underlying temperature stress responses in CAM species.

59 BASIC BIOLOGICAL SCIENCES↗

Temporal X-ray astronomy with a pinhole camera

Preliminary results from the Ariel-5 all-sky X-ray monitor are presented, along with sufficient experiment details to define the experiment sensitivity. Periodic modulation of the X-ray emission was investigated from three sources with which specific periods were associated, with the results that the 4.8 hour variation from Cyg X-3 was confirmed, a long-term average 5.6 day variation from Cyg X-1 was discovered, and no detectable 0.787 day modulation of Sco X-1 was observed. Consistency of the long-term Sco X-1 emission with a shot-noise model is discussed, wherein the source behavior is shown to be interpretable as approximately 100 flares per day, each with a duration of several hours. A sudden increase in the Cyg X-1 intensity by almost a factor of three on 22 April 1975 is reported, after 5 months of relative source constancy. The light curve of a bright nova-like transient source in Triangulum is presented, and compared with previously observed transient sources. Preliminary evidence for the existence of X-ray bursts with duration less than 1 hour is offered.

Holt, S. S.↗

Temporal X-ray astronomy with a pinhole camera

Preliminary results from the Ariel-5 All-Sky X-Ray Monitor are presented, along with sufficient experiment details to define the experiment sensitivity. Periodic modulation of the X-ray emission is investigated from three sources with which specific periods have been associated, with the results that the 4.8 h variation from Cyg X-3 is confirmed, a long-term average 5.6 day variation from Cyg X-1 is discovered, and no detectable 0.787 day modulation of Sco X-1 is observed. Consistency of the long-term Sco X-1 emission with a 'shot-noise' model is discussed, wherein the source behavior is shown to be interpretable as about 100 'flares' per day, each with a duration of several hours. A sudden increase in the Cyg X-1 intensity by almost a factor of three on 22 April 1975 is reported, after 5 months of relative source constancy. The light curve of a bright nova-like transient source in Triangulum is presented, and compared with previously observed transient sources. Preliminary evidence for the existence of X-ray 'bursts' with duration less than 1 h is offered, with the caveat that there is not yet any supporting evidence to guarantee that the effect is truly astronomical.

Holt, S. S.↗

Space telescope, a long-life free flyer

The paper describes NASA's Space Telescope (ST) adapted to Shuttle capabilities for launch and retrieval which utilizes the full Shuttle cargo bay space available for payloads and can be returned to the ground for refurbishment. Its objective is to maximize ST's productive lifetime, to probe the universe, and to analyze light from energy sources which cannot be studied by ground-based telescopes. The Shuttle orbiting lifetime will be extended to at least five years, and scientific instruments or failed spacecraft components will be replaced on-orbit. The ST will be returned to earth for major overhauls, refurbished, and relaunched. In summary, the Shuttle will allow space astronomy to be accomplished in the usual manner - by observing, adjusting, changing detectors, and reobserving. The support systems module, the optical telescope assembly, scientific instruments, including the wide field/planetary camera, the faint object spectrograph and the high speed photometer are described.

Field, E. L.↗

Progress in Acoustic Transmission of Power through Walls

A document presents updated information on implementation of the wireless acoustic-electric feed-through (WAEF) concept, which was reported in Using Piezoelectric Devices To Transmit Power Through Walls (NPO-41157), NASA Tech Briefs, Vol. 32, No. 6 (June 2008), page 70. To recapitulate: In a basic WAEF setup, a transmitting piezoelectric transducer on one side of a wall is driven at resonance to excite ultrasonic vibrations in the wall. A receiving piezoelectric transducer on the opposite side of the wall converts the vibrations back to an ultrasonic AC electric signal, which is then detected and otherwise processed in a manner that depends on the modulation (if any) applied to the signal and whether the signal is used to transmit power, data, or both. The present document expands upon the previous information concerning underlying physical principles, advantages, and potential applications of WAEF. It discusses the design and construction of breadboard prototype piezoelectric transducers for WAEF. It goes on to present results of computational simulations of performance and results of laboratory tests of the prototypes. In one notable test, a 100-W light bulb was lit by WAEF to demonstrate the feasibility of powering a realistic load.

Sherrit,Stewart↗

Short solar events with evidence of repetitive structures

Several short (less than 40 s) solar hard X-ray events (greater than 100 keV) have been observed simultaneously with identical instruments on the Venera 11, 12, 13, and 14 and Prognoz 7 (Franco-Soviet Signe experiments) spacecraft. High time resolution (equal to or greater than 2 ms) data were stored in memory when a trigger occurred. The observations reported here were made by Prognoz 7 and V12 which were closer to the sun at the time and provided good statistics. Observations of modulation with a period of 1.6 s for the event on 1978 December 3 are presented. Also presented is evidence for fast time fluctuations from an event on 1979 November 6, observed with Venera 12, and another on 1981 September 6, observed with the Solar Maximum Hard X-Ray Burst Spectrometer. Power spectrum analysis, epoch folding, and Monte Carlo simulation to evaluate the statistical significance of persistent time delays between features. The results are discussed in light of the MHD model proposed by Zaitsev and Stepanov (1982) and Zaitsev, Stepanov, and Chernov (1984).

Desai, Upendra D.↗

Human Factors in Space Flight

After forty years of experience with human space flight (Table 1), the current emphasis is on the design of space vehicles, habitats, and missions to ensure mission success. What lessons have we learned that will affect the design of spacecraft for future space exploration, leading up to exploring Mars? This chapter addresses this issue in four sections: Anthropometry and Biomechanics; Environmental Factors; Habitability and Architecture; and Crew Personal Sustenance. This introductory section introduces factors unique to space flight. A unique consideration for design of a habitable volume in a space vehicle is the lack of gravity during a space flight, referred to as microgravity. This affects all aspects of life, and drives special features in the habitat, equipment, tools, and procedures. The difference in gravity during a space mission requires designing for posture and motion differences. In Earth s gravity, or even with partial gravity, orientation is not a variable because the direction in which gravity acts defines up and down. In a microgravity environment the working position is arbitrary; there is no gravity cue. Orientation is defined primarily through visual cues. The orientation within a particular crew station or work area is referred to as local vertical, and should be consistent within a module to increase crew productivity. Equipment was intentionally arranged in various orientations in one module on Skylab to assess the efficiency in use of space versus the effects of inconsistent layout. The effects of that arrangement were confusion on entering the module, time spent in re-orientation, and conflicts in crew space requirements when multiple crew members were in the module. Design of a space vehicle is constrained by the three major mission drivers: mass, volume and power. Each of these factors drives the cost of a mission. Mass and volume determine the size of the launch vehicle directly; they can limit consumables such as air, water, and propellant; and they impact crew size and the types of activities the crew performs. Power is a limiting factor for a space vehicle. All environmental features (e.g., atmosphere, temperature, lighting) require power to maintain them. Power can be generated from batteries, from fuel cells, or from solar panels. Each of these sources requires lifting mass and volume from Earth, driving mission cost. All engineering decisions directly impact the design for habitation design and usage. For instance, if fuel cells are used they produce water, which is used for drinking and food preparation. If a different power source is used water has to be carried and stored on the vehicle which then directly impacts the food system choice as well as the launch weight of the vehicle.

Woolford, Barbara J.↗

NASA Tech Briefs, September 2005

Topivs include: Diamond-Coated Carbon Nanotubes for Efficient Field Emission; Improved Anode Coatings for Direct Methanol Fuel Cells; Advanced Ablative Insulators and Methods of Making Them; PETIs as High-Temperature Resin-Transfer-Molding Materials; Stable Polyimides for Terrestrial and Space Uses; Low-Density, Aerogel-Filled Thermal-Insulation Tiles; High-Performance Polymers Having Low Melt Viscosities; Nonflammable, Hydrophobic Aerogel Composites for Insulation; Front-Side Microstrip Line Feeding a Raised Antenna Patch; Medium-Frequency Pseudonoise Georadar; Facilitating Navigation Through Large Archives; Program for Weibull Analysis of Fatigue Data; Comprehensive Micromechanics-Analysis Code - Version 4.0; Component-Based Visualization System; Software for Engineering Simulations of a Spacecraft; LabVIEW Interface for PCI-SpaceWire Interface Card; Path Following with Slip Compensation for a Mars Rover; International Space Station Electric Power System Performance Code-SPACE; Software for Automation of Real-Time Agents, Version 2; Software for Optimizing Plans Involving Interdependent Goals; Computing Gravitational Fields of Finite-Sized Bodies; Custom Sky-Image Mosaics from NASA's Information Power Grid; ANTLR Tree Grammar Generator and Extensions; Generic Kalman Filter Software; Alignment Stage for a Cryogenic Dilatometer; Rugged Iris Mechanism; Treatments To Produce Stabilized Aluminum Mirrors for Cryogenic Uses; Making AlNx Tunnel Barriers Using a Low-Energy Nitrogen-Ion Beam; Making Wide-IF SIS Mixers with Suspended Metal-Beam Leads; Sol-Gel Glass Holographic Light-Shaping Diffusers; Automated Counting of Particles To Quantify Cleanliness; Phase Correction for GPS Antenna with Nonunique Phase Center; Compact Infrasonic Windscreen; Broadband External-Cavity Diode Laser; High-Efficiency Solar Cells Using Photonic-Bandgap Materials; Generating Solid Models from Topographical Data; Computationally Lightweight Air-Traffic-Control Simulation; Spool Valve for Switching Air Flows Between Two Beds; Partial Model of Insulator/ Insulator Contact Charging; Asymmetric Electrostatic Radiation Shielding for Spacecraft; and Reusable Hybrid Propellant Modules for Outer-Space Transport.

Source record↗

Measuring the Cryogenic Optical Alignment Between the Telescope Element and the Instruments Module of the James Webb Space Telescope

The alignment between the Aft Optical Subsystem (AOS) and the Integrated Science Instruments Module (ISIM) is non-adjustable in orbit, so the alignment must be carefully verified in a cryogenic vacuum environment prior to launch. Optical point source locations calibrated by optical metrology instruments are imaged through the AOS onto the Science Instruments to determine focal, lateral, and clock angle alignment. The pupil image of the AOS is overlaid onto the pupil image of the NIRCam to determine the tip and tilt alignment. In addition, an image from fiducial lights at the Primary Mirror checks the pupil alignment between the telescope entrance pupil, the telescope pupil mask, and the NIRCam aperture stop. The image positions are combined to determine the relative alignment between the Optical Telescope Element (OTE) and the ISIM in all six degrees of freedom with corresponding alignment uncertainties. Uncertainties in the position of focused images of the test sources and images from the pupils are derived from sensitivities of an optical model of the system and the Science Instrument sensing capability. Additional uncertainty in the pupil alignment measurement is due to uncertainty in the analytical removal of gravity effects that simulate the on-orbit alignment environment.

Whitman, Tony↗

Plasmon Dynamics Driven by Aggregation of Tris(2,2′-bipyridine)ruthenium(II)-Functionalized Gold Nanoparticles Probed by XANES and Transient Absorption Spectroscopy

Energy conversion dynamics is critical for advancing next-generation photovoltaics, optoelectronics, and light-harvesting technologies. Noble metal plasmonic nanoparticles play a pivotal role as nanoscale electromagnetic confinement structures, driving photon-induced chemical reactions. In this study, we explore the effects of [Ru(bpy) 3 ] 2+ functionalization and aggregation on citrate-capped gold nanoparticles (AuNPs) of 40 and 100 nm diameters, focusing on molecule-plasmon interactions and their influence on electronic and energy dissipation properties. X-ray absorption near-edge spectroscopy (XANES) revealed that [Ru(bpy) 3 ] 2+ functionalization induces controlled aggregation without altering the oxidation state of gold. A more pronounced white-line intensity is observed in 40 nm AuNPs, consistent with greater s–p–d hybridization and a higher density of surface states, likely influenced by both nanoparticle size and aggregation. Transient absorption (TA) spectroscopy highlights faster electron–phonon relaxation dynamics in aggregated 40 nm nanoparticles, which is attributed to increased electron delocalization and more efficient coupling to the phonon bath. In contrast, 100 nm nanoparticles exhibit minimal changes due to a lower degree of aggregation. Interestingly, we observe that enhanced electron–phonon coupling in aggregated nanoparticles coincides with a slowing of electron–electron scattering. These observations suggest a competitive interplay between the two relaxation pathways, where enhanced energy transfer to the lattice in aggregated systems can suppress electronic thermalization. In conclusion, these findings underscore the critical role of nanoparticle size, aggregation, and molecule–surface interactions in modulating plasmonic dynamics and excited-state lifetimes and further provide valuable insights into designing tailored plasmonic systems with transformative potential for sensing, catalysis, and energy conversion.

36 MATERIALS SCIENCE↗