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NASA NTRS2014

ALMA Observations of α Centauri First Detection of Main-Sequence Stars at 3 mm Wavelength

The precise mechanisms that provide the non-radiative energy for heating the chromosphere and the corona of the Sun and those of other stars constitute an active field of research. By studying stellar chromospheres one aims at identifying the relevant physical processes. Defining the permittable extent of the parameter space can also serve as a template for the Sun-as-a-star. This feedback will probably also help identify stars that potentially host planetary systems that are reminiscent of our own. Earlier observations with Herschel and APEX have revealed the temperature minimum of Alpha Cen, but these were unable to spatially resolve the binary into individual components. With the data reported in this Letter, we aim at remedying this shortcoming. Furthermore, these earlier data were limited to the wavelength region between 100 and 870 um. In the present context, we intend to extend the spectral mapping (SED) to longer wavelengths, where the contrast between stellar photospheric and chromospheric emission becomes increasingly evident. The Atacama Large Millimeter submillimeter Array (ALMA) is particularly suited to point sources, such as unresolved stars. ALMA provides the means to achieve our objectives with both its high sensitivity of the collecting area for the detection of weak signals and the high spatial resolving power of its adaptable interferometer for imaging close multiple stars. This is the first detection of main-sequence stars at a wavelength of 3 mm. Furthermore, the individual components of the binary Alpha CenAB are clearly detected and spatially well resolved at all ALMA wavelengths. The high signal-to-noise ratios of these data permit accurate determination of their relative flux ratios, i.e., S(sub y(sup B)) / S(sub y(sup A))> = 0.54 +/- 0.04 at 440 μm, = 0.46 +/- 0.01 at 870 μm, and = 0.47 +/- 0.006 at 3.1 mm, respectively.. The previously obtained flux ratio of 0.44+/-0.18, which was based on measurements in the optical and at 70 μm, is consistent with the present ALMA results, albeit with a large error bar. The observed 3.1 mm emission greatly exceeds what is predicted from the stellar photospheres, and undoubtedly arises predominantly as free-free emission in the ionized chromospheric plasmas of both stars. Given the distinct difference in their cyclic activity, the similarity of their submm SEDs appears surprising.

Herschel↗

NASA NTRS2019

Simultaenous Retrieval of Surface Roughness Parameters from Combined Active-Passive SMAP Observations

Soil roughness strongly influences processes like erosion, infiltration, moisture and evaporation of soils as well as growth of agricultural plants. An approach to soil roughness based on active-passive microwave covariation is proposed in order to simultaneously retrieve the vertical RMS height (s) and horizontal correlation length (l) of soil surfaces from simultaneously measured radar and radiometer microwave signatures. The approach is based on a retrieval algorithm for active-passive covariation including the improved Integral Equation Method (I2EM). The algorithm is tested with the global active-passive microwave observations of the SMAP mission. The developed roughness retrieval algorithm shows independence of permittivity for > 10 [-] due to the covariation formalism. Results reveal that s and l can be estimated simultaneously by the proposed approach since surface patterns of non-vegetated areas become evident on global scale. In regions with sandy deserts, like the Sahara or the outback in Australia, determined and confirm rather smooth to semi-rough surface roughness patterns with small vertical RMS heights and corresponding higher horizontal correlation lengths.

correlation length↗

NASA NTRS2020

Simultaneous Retrieval of Surface Roughness Parameters for Bare Soils from Combined Active-Passive Microwave SMAP Observations

An active-passive microwave retrieval algorithm for simultaneous determination of soil surface roughness parameters [vertical root-mean-square (RMS) height (s) and horizontal correlation length (l)] is presented for bare soils. The algorithm is based on active-passive microwave covariation, including the improved Integral Equation Method (I²EM), and is tested with global soil moisture active passive (SMAP) observations. The estimated retrieval results for s and l are overall consistent with values in the literature, indicating the validity of the proposed algorithm. Sensitivity analyses showed that the developed roughness retrieval algorithm is independent of permittivity for εₛ > 10 [-]. Furthermore, the physical model basis of this approach (I²EM) allows the application of different autocorrelation functions (ACF), such as Gaussian and exponential ACFs. Global roughness retrieval results confirm bare areas in deserts such as Sahara or Gobi. However, the type of ACF used within roughness parameter estimation is important. Retrieval results for the Gaussian ACF describe a rougher surface than retrieval results for the exponential ACF. No correlations were found between roughness results and the amount of precipitation or the soil texture, which could be due to the coarse spatial resolution of the SMAP data. The extension of this approach to vegetated soils is planned as an add-on study.

correlation length↗

NASA NTRS2019

Developing a soil inversion model framework for regional permafrost monitoring

Currently, the community lacks capabilities to assess and monitor landscape scale permafrost active layer dynamics over large extents. To address this need, we developed a concept of a remote sensing based Soil Inversion Model for regional Permafrost (SIM-P) monitoring. The current SIM-P framework includes a satellite-based soil process model and a soil dielectric model. We are also working on incorporating a radar scattering model for Arctic tundra into the SIM-P framework. A unified soil parameterization scheme was developed to harmonize key soil thermal, hydraulic and dielectric parameters in the soil process and radar models that can be used in the joint soil-radar inversion framework. The soil parameter retrievals of the SIM-P framework include soil organic content (SOC) and active layer thickness (ALT). Initial tests of SIM-P using in-situ soil permittivity observations showed reasonable accuracy in predicting site-level SOC and soil temperature profiles at an Alaska tundra site and ALT in Arctic Alaska. SIM-P will be further tested using airborne P- and L-band radar data collected during NASA’s Arctic Boreal Vulnerability Experiment (ABoVE) to evaluate the sensitivity of longwave radar to active layer properties.

Miller, Charles E.↗

NASA NTRS2020

Simultaneous Retrieval of Surface Roughness Parameters for Bare Soils From Combined Active–Passive Microwave SMAP Observations

An active–passive microwave retrieval algorithm for simultaneous determination of soil surface roughness parameters [vertical root-mean-square (RMS) height ( s ) and horizontal correlation length ( l )] is presented for bare soils. The algorithm is based on active–passive microwave covariation, including the improved Integral Equation Method (I(exp 2) EM), and is tested with global soil moisture active passive (SMAP) observations. The estimated retrieval results for s and l are overall consistent with values in the literature, indicating the validity of the proposed algorithm. Sensitivity analyses showed that the developed roughness retrieval algorithm is independent of permittivity for E(sub s) > 10 [-]. Furthermore, the physical model basis of this approach (I(exp 2) EM) allows the application of different autocorrelation functions (ACF), such as Gaussian and exponential ACFs. Global roughness retrieval results confirm bare areas in deserts such as Sahara or Gobi. However, the type of ACF used within roughness parameter estimation is important. Retrieval results for the Gaussian ACF describe a rougher surface than retrieval results for the exponential ACF. No correlations were found between roughness results and the amount of precipitation or the soil texture, which could be due to the coarse spatial resolution of the SMAP data. The extension of this approach to vegetated soils is planned as an add-on study.

Correlation length↗

NASA NTRS2021

Radar-Sounding Characterization of the Subglacial Groundwater Table Beneath Hiawatha Glacier, Greenland

Radar-sounding surveys associated with the discovery of a large impact crater beneath Hiawatha Glacier, Greenland, revealed bright, flat subglacial reflections hypothesized to originate from a subglacial groundwater table. We test this hypothesis using radiometric and hydrologic analysis of those radar data. The dielectric loss between the reflection from the top of the basal layer and subglacial reflection and their reflectivity difference represent dual constraints upon the complex permittivity of the basal material. Either ice-cemented debris or fractured, well-drained bedrock explain the basal layer's radiometric properties. The subglacial reflector's geometry is parallel to isopotential hydraulic head contours, located 7.5–15.3 m below the interface, and 11 ± 7 dB brighter than the ice–basal layer reflection. We conclude that this subglacial reflection is a groundwater table and that its detection was enabled by the wide bandwidth of the radar system and unusual geologic setting, suggesting a path for future direct radar detection of subglacial groundwater elsewhere.

Johnathan T. Bessette↗

NASA NTRSDate not supplied

Microwave Structure Construction Capability Year One Accomplishments

The Microwave Structure Construction Capability (MSCC) element, part of the Moon to Mars Planetary Autonomous Construction Project (MMPACT) was initiated in 2020. MSCC is responsible for creating horizontal and vertical infrastructure on the moon using microwave energy. Microwave energy was selected since it is the only method to volumetrically heat the regolith. All other sintering/melting methods rely on thermal conduction through the very low conductivity surface, resulting in an inefficient process. Advances were achieved in materials characterization and understanding, microwave sintering in vacuum, and microwave design and analyses. Two dielectric property testing systems have been developed at Radiance Technologies and JPL. These will examine dielectric properties at cryogenic temperatures and over a broad frequency range. Permittivity and permeability testing at -60 ̊C in vacuum from 0.05 to 3 GHz has been generated at JPL. Additional modifications will be made to go to -190 ̊C (LN2). Radiance Technologies created a test system to measure dielectric properties at greater than 10 GHz and initiated work on developing a vacuum capable, portable test system to measure dielectric properties of Apollo regolith and simulants from 100 MHz to 18 GHz. These tests are to identify optimal heating frequencies and protocols. During microwave sintering at about 1100 ̊C, volatiles were creating difficulty in achieving a reasonably dense specimen. Due to processing in vacuum and the nature of the lunar regolith, some volatiles and porosity are expected. However, the Earth produced simulants have non-lunar materials in them that create volatiles that aren’t representative of lunar regolith. Therefore, a five month effort was conducted to establish a heat treat method to remove these non-lunar materials. Tests were conducted using TGA mass spectrometry, heating in vacuum and conducting mass spectrometry, dielectric and DTA, Raman, BET, particle size analysis, morphological analysis, carbon and sulfur chemical content determination and microscopy. The process has been scaled-up to 6 kg batch size and undergoing evaluation. A 36 kg batch size is the target for JSC-1A and other limited availability simulants. These calcining protocols will be standard for NASA and beyond. MSCC has also created scalable processes for fabricating synthetic lunar materials. Processes to fabricate Anorthite (plagioclase CaAl2Si2O8), Diopside (pyroxene CaMgSi₂O₆), and Enstatite (pyroxene Mg2Si2O6) have been generated. These materials will enable generation of microwave sintering models to bound various composition ranges anticipated on the Moon, therefore mitigating the need for a precise simulant with respect to location on the Moon. Successful microwave sintering in air using a horn applicator was demonstrated. All previous microwave vacuum sintering in the literature was at small scale and in a contained enclosure thus taking advantage of reflections. This is the first to use a lunar like microwave applicator to sinter ceramic in a bed as it would be done on the Moon. Small scale and inert sintering were conducted to assist in developing protocols with quicker turnaround times than larger scale testing. Testing has anchored thermal analysis predicting heat flow in vacuum during microwave sintering. Thermal conductivity testing was also initiated. Microwave coupling to the regolith has been modeled by multiple organizations and with different software packages. At least six horn designs and applicator configurations for both magnetron and solid state sources are being examined. Optimal simulant container designs for microwaves have also been generated. The power and electronics design for the solid state microwave system has been initiated. Concept designs for a lander based microwave sintering have been evaluated.

microwave↗

NASA NTRS2021

A 1-D Submm-wave Leaky-Wave Phased Array using MEMS Phase Shifters

Beam-scanning of submillimeter-wave spectrometers and radiometers have traditionally been implemented using mechanical scanning mechanisms due to the absence of lowloss electronic phase shifters. Recently developed waveguideintegrated MEMS phase shifters are paving the way to realize electronic beam-steering using submm-wave phased arrays. In this work, two phased array demonstrators are presented that operate from 500GHz to 600GHz. A 20 dB directivity 8 ? 1 leaky-wave antenna array will be demonstrated, using fixed waveguide feeding networks, to be capable of ?20? scanning with a scan loss less than 1:7 dB. Secondly, an equivalent but smaller 17 dB directivity 4 ? 1 array will be integrated with MEMS phase shifters to demonstrate a dynamic scanning capability over a ?9:5? range. The antenna array is based on closely sampled square waveguides, terminated with a double-iris, in close proximity of a low permittivity superstrate in order to reduce the grating lobes at larger scanning angles. Measurements are expected to be presented at the conference.

Chattopadhyay, Goutam↗

NASA NTRSDate not supplied

LIRA: Probing the Lunar Surface for Resources.

The thermal, compositional and electrical properties of the lunar regolith, such as the triboelectric properties of lunar dust, the volatile content and the thermophysical properties of the polar regolith are essential to understand from a scientific perspective as well as for resource extraction and hazard mitigation. Understanding these properties specifically requires in situ measurement, as these properties are inherent in the ambient environment. With the Lunar In situ Regolith Analyzer (LIRA) we will combine mature surface sensor technologies from previous spacecraft missions (TECP) with new sensors (ClO4- ) and battery capability to achieve a compact in situ analysis package. The surface instrument suite is adapted for lunar conditions from a sensor developed as part of the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the 2007 Mars Phoenix mission, as well as supplemental sensors. • The Thermal and Electrical Conductivity Probe (TECP), flown on MECA/Phoenix, which measures heat capacity, thermal conductivity, electrical resistance, and electrical permittivity between needles inserted into the soil. The TECP also measured atmospheric humidity, a capability that will be retained to search for subsurface H2O ice. The Mars TECP weighed 100-gram and by definition was at TRL 9. The lunar version (LIRA) is TRL 4. • The Perchlorate (ClO4) sensor is based on the fluorescence property of perchlorate (Mg, Fe, Na). We added a light source to excite the perchlorate (ClO4) and a photo diode to collect the emission wavelength. A sun-shade over the photo diode blocks out the ambient light during day light hours. The unifying goal of LIRA is to deliver a complete, integrated experiment suite that investigates properties that must be measured in situ, and provides the capability to power the suite at night or in PSRs, as well as a means to simulate aspects of the diurnal transition by delivering an optical pulse to the surface with intensity comparable to sunlight. We describe the scientific context of LIRA, touching on the electrical state of the near-surface environment, the thermal properties of the undisturbed regolith, and the distribution, geochemistry, and mobility of water. We also address the exploration implications of the work, examining hazards and resources in the context of strategic knowledge gaps (SKGs).

Heather Smith↗

NASA NTRS2023

New Seawater Dielectric Constant Parametrization and Application to SMOS Retrieved Salinity

The accuracy of the Sea Surface Salinity (SSS) retrieved from L-Band radiometer measurements is strongly dependent on the reliability of the dielectric constant model. Two new parametrizations were recently developed based on one hand on the Soil Moisture and Ocean Salinity (SMOS) satellite multi-angular brightness temperature measurements by Boutin et al. (2021) (BV), and on the other hand, on new George Washington University laboratory measurements by Zhou et al. (2021) (GW2020). These two approaches are fully independent. For most SSS and Sea Surface Temperature (SST) conditions commonly observed over the open ocean, the relative variations of brightness temperatures Tb simulated through the BV and GW2020 parametrizations agree particularly well, and better than with earlier parametrizations previously used in the SMOS, Soil Moisture Active Passive (SMAP) and Aquarius SSS retrievals. Nevertheless, uncertainty remains, especially below 10 °C where a ∼ 0.1 K relative difference between the two models is observed. This motivates the development of a revised parameterization, BVZ, based on a methodology similar to that used to derive BV but using GW2020 instead of SMOS measurements. Compared to the GW2020 parameterization, BVZ is derived with a reduced number of degrees of freedom, it relies on the TEOS10 PSS78 conductivity-salinity relationship, and on the previously derived static permittivity of fresh water. One month per season of SMOS data have been reprocessed in 2018 using BV, GW2020, and BVZ. We find the best overall agreement between SMOS SSS and Argo SSS with BVZ parametrization, with noticeable improvement in the 5 °C–15 °C SST range.

sea measurements↗

NASA NTRSDate not supplied

3D Microwave Imaging of Impact Damage in Composites

This presentation presents the results of detecting impact damage in woven composites using a 3D microwave imaging system. The microwave results are compared to laser scanner results. After demonstrating the system on two composite samples, the multi-functionality of the system is discussed. They microwave systems ability to detect changes in permittivity of dielectrics is demonstrated by imaging RTV underneath space shuttle tiles, and the detection of sintered regolith simulant when buried in loose regolith simulant.

William (Cy) Wilson↗

NASA NTRS2024

Characterization of NUW-LHT-5m, A Lunar Highland Simulant

A new simulant of the lunar highlands regolith, NUW-LHT-5M, was designed by NASA and manufactured by Washington Mills. The simulant was based on Apollo 16 data and is a member of the NU-LHT-series. NASA’s Marshall Space Flight Center and Johnson Space Center have already purchased 3 metric tons of the simulant for advanced engineering work. In support of engineering uses of the simulant, we provided measurements of the simulant including: mineral abundance and composition, liberation, X-ray fluorescence (XRF), ferrous iron, carbon, sulfur, 60 element inductively coupled plasma (ICP), loss on ignition, particle size, both 2D and 3D particle shape, specific surface area, shear, cohesion, internal friction, helium pycnometry, minimum index density, tap density, magnetic susceptibility, cryogenic and high temperature permittivity, visible and near-infrared (VNIR) and middle infra-red spectroscopy (MIR), differential scanning calorimetry (DSC), viscosity, thermal diffusivity, thermal conductivity, thermal gravimetric analysis (TGA), evolved gas analysis (EGA), and spark sintering. For the crystalline components the design of the simulant called for two rocks from the Stillwater Complex, Montana: 17.6 wt% norite, 37.7% anorthosite, and 4.7 wt% olivine from an unspecified commercial source. The other 40% of the simulant was a high calcium (An100), vesicular glass that Washington Mills made specifically for the simulant. Fabrication and quality control processes for both the glass and the simulant are described. Importantly, most of the graphs and tables presented herein provide values for both the new simulant and data for the older NASA mare simulant, JSC-1A. Finally, we discussed the current limitations of NUW-LT-5M and most other lunar regolith simulants to replicate the lunar material.

lunar regolith simulant↗

NASA NTRS2024

Mapping Ice Buried by the 1875 and 1961 Tephra of Askja Volcano, Northern Iceland using Ground-Penetrating Radar: Implications for Askja Caldera as a Geophysical Testbed for In-Situ Resource Utilization

Eruptions of the Askja Volcano in Northern Iceland in 1875 and 1961 blanketed the caldera with rhyolitic and basaltic tephra deposits, respectively, which preserved layers of seasonal snowpack as massive ice. Askja serves as an operational and geophysical analog to test ground-penetrating radar field and analysis techniques for in-situ resource utilization objectives relevant to the martian and lunar environments. We conducted ground-penetrating radar surveys at center frequencies of 200, 400, and 900 MHz to map the thickness and extent of tephra deposits and underlying massive ice at three caldera sites. We identified up to 1 meter of tephra preserving up to 4.5 meters of massive ice. We measured the real dielectric permittivity of the overlying tephra and the total attenuation at each frequency of the tephra and ice. A key objective of our investigation was to determine if this attenuation (or loss) could be used as an additional, identifying characteristic of massive ice preserved at depth when compared to ice-free stratigraphy. Loss rates of the ice-rich subsurface decreases with increasing ice thickness relative to the overburden which may constitute a possible signature. Attenuation also increased with increasing frequency. The tephra, ice, and other volcanic deposits at each of our three caldera sites and the ice-free pumice-mantled 1961 Vikrahraun lava flow exhibited a characteristically low loss rate at all frequencies. This result highlights the ambiguity associated with identifying the unique signature of ice within low-loss stratigraphies, a possible challenge for its identification in the martian or lunar subsurface using radar.

Emileigh S. Shoemaker↗

NASA NTRS2024

Direct Ink Write 3D Printing of Fully Dense and Functionally Graded Liquid Metal Elastomer Foams

Liquid metal (LM) elastomer composites offer promising potential in soft robotics, wearable electronics, and human-machine interfaces. Direct ink write (DIW) 3D printing offers a versatile manufacturing technique capable of precise control over LM microstructures, yet challenges such as interfilament void formation in multilayer structures impact material performance. Here, a DIW strategy is introduced to control both LM microstructure and material architecture. Investigating three key process parameters–nozzle height, extrusion rate, and nondimensionalized nozzle velocity–it is found that nozzle height and velocity predominantly influence filament geometry. The nozzle height primarily dictates the aspect ratio of the filament and the formation of voids. A threshold print height based on filament geometry is identified; below the height, significant surface roughness occurs, and above the ink fractures, which facilitates the creation of porous structures with tunable stiffness and programmable LM microstructure. These porous architectures exhibit reduced density and enhanced thermal conductivity compared to cast samples. When used as a dielectric in a soft capacitive sensor, they display high sensitivity (gauge factor = 9.0), as permittivity increases with compressive strain. These results demonstrate the capability to simultaneously manipulate LM microstructure and geometric architecture in LM elastomer composites through precise control of print parameters, while maintaining geometric fidelity in the printed design.

Spencer Pak↗

DOE OSTI2021

Electroabsorption optical modulator

An electroabsorption modulator that operates based on electroabsorption of a surface plasmon polariton mode is improved by various structural changes and/or selection of different materials. For example, at least a portion of the waveguide may be made to be conductive, e.g., by doping. Also, layers that make up the modulator structure may be placed along sides of waveguides in addition to or instead of simply on the top thereof. High permittivity gate dielectric materials may be employed. Also, materials other than ITO may be employed as a transparent conductor. Such an improved plasmonic electroabsorption modulator can be fabricated using standard semiconductor processing techniques and may be integrated with standard photonic integrated circuits, including silicon photonics and compound semiconductor-based platforms. Advantageously, high-speed, low-voltage operation over a wide spectrum of wavelengths may be achieved.

Wood, Michael↗

DOE OSTI2023

Chapter 14: Surface plasmon resonance enhanced artificial photosynthesis of chemical fuels for energy storage

Nanostructured noble metals such as Au, Ag, and Cu have interesting optical properties because of the oscillation motions of their surface electrons upon strong coupling with light under resonance conditions. This resonant oscillation motion of conduction electrons refers to surface plasmon resonance (SPR) and localized SPR (LSPR) when localized near the surface of a nanoparticle. The extinction spectrum of a solution of plasmonic nanoparticles has tunable wavelength responses from UV to NIR due to strong light scattering and absorption which are highly sensitive to the permittivity of the nanoparticles, their sizes and shapes, and chemical environment. Strong light scattering due to the LSPR of plasmonic nanoparticles creates a strong localized and far-field intensity capable of enhancing light absorption characteristics of a chromophore near a plasmonic surface. Engineering the chromophores’ radiative decay dynamics can be done by 1) increasing its radiative decay rate to increase its photoluminescence intensity and 2) increasing its nonradiative decay rates associated to direct charge transfer to the metal surface. Such interesting photophysical properties of a chromophore can be extended to other light-absorbing materials such as semiconductor thin films and nanostructures. This plasmonic effect on the photophysics of a light-absorbing material can be theoretically and experimentally validated. The phenomenon has also been applied to advanced optoelectronic devices such as organic light-emitting diodes (OLED)1 and organic photovoltaics (OPV).2-4 The local field created by the SPR can provide an intense EM field to enhance photoluminescence emission of an organic chromophore5-8 and Raman scattering of an organic molecule, and single-molecule Raman9-10 can be detected on specially designed LSPR substrate. (Figure 1 on SPR for energy) Recent studies suggest that LSPR can be incorporated in light-harvesting and conversion systems to increase energy conversion in a solar cell and photoelectrochemical cell and chemical transformations of CO2 to chemical fuels.11-12 Plasmonic active metals naturally exhibit catalytic activities for electrochemical fuel conversion that can be enhanced by engineering their structures to form unique catalytic structures such as symmetry-broken Au-Cu Janus nanocrystals.13 These studies are critical to addressing the global challenges of energy14-15 and CO2 emission from nonrenewable sources such as coal, petroleum, and natural gas.16-17 Electrochemical systems comprised of unique photonic structures and functions that enable efficient and affordable energy harvesting/conversion/storage are highly desired for providing safe and environment-friendly energy sources. This chapter reviews our recent work of LSPR enabled photoelectrochemical water splitting and recent advances in LSPR-enabled CO2 reduction and photochemical reactions reported in the literature. Scientific and technical challenges of applying LSPR to enhance these energy conversion and storage systems are discussed at the conclusion of this chapter.

Pan, Shanlin↗

DOE OSTI2022

Pareto Optimization of Oligomer Polarizability and Dipole Moment Using a Genetic Algorithm

High-performance electronic components are highly sought after in order to produce increasingly smaller and cheaper electronic devices. Drawing inspiration from inorganic dielectric materials, in which both polarizability and polarization contribute, organic materials can also maximize both. For a large set of small molecules drawn from PubChem, a Pareto-like front appears between the polarizability and dipole moment, indicating the presence of an apparent trade-off between these two properties. We tested this balance in π-conjugated materials by searching for novel conjugated hexamers with simultaneously large polar- izabilities and dipole moments with potential use for dielectric materials. Using a genetic algorithm (GA) screening technique in conjunction with an approximate density functional tight-binding method for property calculations, we were able to efficiently search chemical space for optimal hexamers. Given the scope of chemical space, using the GA technique saves considerable time and resources by speeding up molecular searches compared to a systematic search. Here, we also explored the underlying structure–function relationships, including sequence and monomer properties, that characterize large polarizability and dipole moment regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Ion-Pair Reorganization Regulates Reactivity in Photoredox Catalysts

Cyclometalated and polypyridyl complexes of d6 metals are promising photoredox catalysts, using light to drive reactions with high kinetic or thermodynamic barriers via the generation of reactive radical intermediates. However, while tuning of their redox potentials, absorption energy, excited-state lifetime and quantum yield are well-known criteria for modifying activity, other factors could be important. Here we show that dynamic ion-pair reorganization controls the reactivity of a photoredox catalyst, [Ir[dF(CF3)ppy]2(dtbpy)]X. Time-resolved dielectric-loss experiments show how counter-ion identity influences excited-state charge distribution, evincing large differences in both the ground- and excited-state dipole moment depending on whether X is a small associating anion (PF6-) that forms a contact-ion pair versus a large one that either dissociates or forms a solvent-separated pair (BArF4-). These differences correlate with the reactivity of the photocatalyst toward both reductive and oxidative electron transfer, amounting to a 4-fold change in selectivity toward oxidation versus reduction. These results suggest that ion pairing could be an underappreciated factor that modulates reactivity in ionic photoredox catalysts.

catalysis↗