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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Pair of TESS Planets Spanning the Radius Valley around the Nearby Mid-M Dwarf LTT 3780

We present the confirmation of two new planets transiting the nearby mid-M dwarf LTT 3780 (TIC 36724087, TOI-732, V = 13.07, K {sub s} = 8.204, R {sub s} = 0.374 R {sub ⊙}, M {sub s} = 0.401 M {sub ⊙}, d = 22 pc). The two planet candidates are identified in a single Transiting Exoplanet Survey Satellite sector and validated with reconnaissance spectroscopy, ground-based photometric follow-up, and high-resolution imaging. With measured orbital periods of P {sub b} = 0.77, P {sub c} = 12.25 days and sizes r {sub p,b} = 1.33 ± 0.07, r {sub p,c} = 2.30 ± 0.16 R {sub ⊕}, the two planets span the radius valley in period–radius space around low-mass stars, thus making the system a laboratory to test competing theories of the emergence of the radius valley in that stellar mass regime. By combining 63 precise radial velocity measurements from the High Accuracy Radial velocity Planet Searcher (HARPS) and HARPS-N, we measure planet masses of m{sub p,b}=2.62{sub −0.46}{sup +0.48} and m{sub p,c}=8.6{sub −1.3}{sup +1.6} M {sub ⊕}, which indicates that LTT 3780b has a bulk composition consistent with being Earth-like, while LTT 3780c likely hosts an extended H/He envelope. We show that the recovered planetary masses are consistent with predictions from both photoevaporation and core-powered mass-loss models. The brightness and small size of LTT 3780, along with the measured planetary parameters, render LTT 3780b and c as accessible targets for atmospheric characterization of planets within the same planetary system and spanning the radius valley.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Modeling the Effects of Drift Orbit Bifurcation on Radiation Belt Electrons

Abstract Drift orbit bifurcation (DOB) has been suggested to play a major role in the loss and transport of radiation belt electrons since it violates the second adiabatic invariants of particles and makes the third invariant undefined. Results from our guiding‐center test particle simulations using the Tsyganenko‐1989c magnetic field model show that the DOB could affect a broad region of the outer radiation belt, which can penetrate inside the geosynchronous orbit at Kp ≥ 3, and its effects are more significant further away from the Earth, at a higher Kp and for higher electron energies. Specifically, the short‐term simulation results after one electron drift show both traditional and nontraditional DOB transport of electrons, with the nontraditional DOB, caused by a third minimum of the magnetic field strength near the equator, reported here for the first time. Moreover, our results show large ballistic jumps in the second invariant and radial distance for electrons at high equatorial pitch angles after one drift. In addition, long‐term DOB transport coefficients of electrons over many drifts are calculated based on our simulation results. We find that the pitch angle and radial diffusion coefficients of electrons due to DOB could be comparable to or even larger than those caused by electron interactions with chorus and Ultra‐Low‐Frequency waves, respectively. In sum, our results demonstrate that DOB could cause effective loss and transport of radiation belt electrons even in the absence of waves.

Astronomy & Astrophysics↗
DOE OSTI2021

The Atacama Cosmology Telescope: A Search for Planet 9

We use Atacama Cosmology Telescope (ACT) observations at 98 GHz (2015–2019), 150 GHz (2013–2019), and 229 GHz (2017–2019) to perform a blind shift-and-stack search for Planet 9. The search explores distances from 300 au to 2000 au and velocities up to 6farcm3 per year, depending on the distance (r). For a 5 Earth-mass Planet 9 the detection limit varies from 325 au to 625 au, depending on the sky location. For a 10 Earth-mass planet the corresponding range is 425 au to 775 au. The predicted aphelion and most likely location of the planet corresponds to the shallower end of these ranges. The search covers the whole 18,000 square degrees of the ACT survey. No significant detections are found, which is used to place limits on the millimeter-wave flux density of Planet 9 over much of its orbit. Overall we eliminate roughly 17% and 9% of the parameter space for a 5 and 10 Earth-mass Planet 9, respectively. These bounds approach those of a recent INPOP19a ephemeris-based analysis, but do not exceed it. We also provide a list of the 10 strongest candidates from the search for possible follow-up. More generally, we exclude (at 95% confidence) the presence of an unknown solar system object within our survey area brighter than 4–12 mJy (depending on position) at 150 GHz with current distance 300 au < r < 600 au and heliocentric angular velocityy <?CDATA $1\buildrel{\,\prime}\over{.} 5\,{\mathrm{yr}}^{-1}\lt v\cdot \tfrac{500\,\mathrm{au}}{r}\lt 2\buildrel{\prime\prime}\over{.} 3\,{\mathrm{yr}}^{-1}$?> 1 .' 5 yr – 1 < v · 500 au r < 2 ." 3 yr – 1 , corresponding to low-to-moderate eccentricities. These limits worsen gradually beyond 600 au, reaching 5–15 mJy by 1500 au.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Candidate spin-liquid ground state in CsNdSe 2 with an effective spin-1/2 triangular lattice

Rare-earth-based triangular lattice materials are extremely attractive for studying unconventional magnetism. Here, we report the magnetic properties of layered CsNdSe 2 based on direct current (DC) and alternating current (AC) susceptibility measurements down to 0.04 K. While the AC susceptibility at the zero DC field shows a broad hump below 0.5 K, there is no sign of any long-range magnetic ordering. Quantitative analysis of the DC magnetic susceptibility gives the negative Curie-Weiss (CW) temperature θ CW < 0 in all directions, indicating antiferromagnetic interaction between Nd ions. Of particular interest is the low temperature magnetic susceptibility, which reflects the effective spin-1/2 state with $\theta^a_{\text {cw}}/\theta^c_{\text {cw}}$ > 3. The estimated exchange interactions are J a /k B = 1.42 K (in-plane) and J c /k B = 0.44 K (out-of-plane), pointing to the anisotropic magnetism. First-principles calculations that include spin-orbit coupling and Coulomb correlations reveal multiple states with zero net magnetization for CsNdSe 2 . Both experiment and simulation strongly suggest CsNdSe 2 has the spin liquid ground state with effective spin-1/2. Application of a magnetic field can induce long-range antiferromagnetic ordering with the maximum transition temperature around 0.3 K, in further support of the zero-field spin liquid state.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Epitaxial Er-doped Y 2 O 3 on silicon for quantum coherent devices

Rare-earth ions have incomplete 4f shells and possess narrow optical intra-4f transitions due to shielding from electrons in the 5s and 5p orbitals, making them good candidates for solid-state optical quantum memory. The emission of Er 3+ in the telecom C-band (1530 nm – 1565 nm) makes it especially attractive for this application. In order to build practical, scalable devices, the REI needs to be embedded in a non-interacting host material, preferably one that can be integrated with silicon. In this paper, we show that Er 3+ can be isovalently incorporated into epitaxial Y 2 O 3 thin films on Si (111). We report on the synthesis of epitaxial, single-crystalline Er:Y 2 O 3 on Si with a narrow inhomogeneous linewidth in the photoluminescence spectra, 5.1 GHz (<100 mK) and an optical excited state lifetime of 8.1 ms. The choice of Y 2 O 3 was driven by its low nuclear spin and small lattice mismatch with Si. Using photoluminescence (PL) and electron paramagnetic resonance, we show that Er 3+ substitutes for Y in the crystal lattice. The role of interfacial SiO x , diffusion of silicon into the film, and the effect of buffer layers on inhomogeneous PL linewidth are examined. We also find that the linewidth decreased monotonically with film thickness but surprisingly exhibits no correlation with the film crystalline quality as measured by the x-ray rocking curve scans suggesting other factors at play that limit the inhomogeneous broadening in Y 2 O 3 films.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Magnetic properties of Tm 3+ in layered triangular lattices

Rare-earth chalcogenides, ARCh 2 (A = alkali metal or monovalent ion; R = rare-earth elements; Ch = O, S, and Se), have been identified as promising candidates for exploring a variety of novel frustrated quantum magnetic phenomena. Tm-based series, ATmCh 2 , where Tm 3+ ions are arranged on various frustrated geometric lattices, provide a platform for investigating the competitions among spin–orbit coupling, crystal field effects, and magnetic exchange interactions in the context of geometric frustration. In this study, we present how the crystallographic structures of newly synthesized ATmSe 2 (A = Li and Na) influence their frustrated magnetic behaviors. Both NaTmSe 2 and LiTmSe 2 adopt a delafossite-type structure with a two-dimensional (2D) triangular lattice, but LiTmSe 2 has a much shorter c-axis parameter compared to this in NaTmSe 2 . Both heat capacity and magnetic susceptibility measurements confirm the absence of long-range magnetic order in either compound. However, magnetic measurements data reveals the differences in magnetic interactions: NaTmSe 2 exhibits features of low-dimensional magnetism, likely driven by its layered crystal structure, compared to LiTmSe 2 .

Crystal field theory↗
DOE OSTI2022

Orbital stability analysis of hypothetical Earth-mass and Luna-mass moons in the Sagarmatha (HD 100777) star system

Abstract Six of the solar system planets have 150 confirmed moons (Earth—1, Mars—2, Jupiter—53, Saturn—53, Uranus—27, Neptune—14) and seven of them (Ganymede, Titan, Callisto, Io, the Moon, Europa, Triton) have masses >0.001 $M_\oplus$. However, no exomoons have yet been discovered despite the successful detection of ∼5000 exoplanets. We can infer, based on the solar system planets, that these exoplanets are capable of hosting one or more exomoons. In this paper, we study the possible existence of hypothetical Earth-mass and Luna-mass moons orbiting the Jupiter-mass planet, Laligurans (HD 100777b) in the Sagarmatha (HD 100777) star system by means of orbital stability. We apply long-term orbital integrations and the MEGNO (mean exponential growth of nearby orbits) chaos indicator to study the orbital stability of the moons and predict a phase-space region comprising periodic, chaotic, and unstable orbits. The phase spaces primarily constitute the moon's semimajor axis, which extends from the host planet's Roche radius to the Hill radius, and full range of eccentricity. Specific points are picked from three different regions of the MEGNO map and run as single-orbit integration for up to 10 billion periods of the innermost orbit. Furthermore, the lifetime and maximum eccentricity maps are generated from the direct integration to inspect the stable and unstable orbital configurations. The analyses of these maps, with the aid of time-series plots, show that both moons maintain stable orbits in the low-eccentricity regime and semimajor axis between the Roche limit and 28.4% of the Hill radius of the planet.

Gautam, Aayush (ORCID:0000000247257589)↗
DOE OSTI2021

Refined Telluric Absorption Correction for Low-resolution Ground-based Spectroscopy: Resolution and Radial Velocity Effects in the O{sub 2}A-band for Exoplanets and K i Emission Lines

Telluric correction of spectroscopic observations is either performed via standard stars that are observed close in time and airmass along with the science target, or recently growing in importance, by theoretical telluric absorption modeling. Both approaches work fine when the telluric lines are resolved, i.e., at a spectral resolving power larger than about 10,000, and it is sufficient to facilitate the detection of spectral features at lower resolution. However, a meaningful quantitative analysis also requires the reliable recovery of line strengths. Here, we show for the Fraunhofer A-band of molecular O{sub 2} that the standard telluric correction approach fails in this at lower spectral resolutions, as an example for the general problem. Doppler-shift-dependent errors of the restored flux may arise, which can amount to more than 50% in extreme cases, depending on the line shapes of the target spectral features. Two applications are discussed: the recovery of the O{sub 2} band in the reflected light of an Earth analog atmosphere, as facilitated potentially in the future using an orbiting starshade and a ground-based extremely large telescope; and the recovery of the intrinsic ratio of the K i lines in the post-nova V4332 Sgr tracing the optical depth of the emitting region, to exemplify the relevance using present-day instrumentation. We show how one should derive correction functions for the compensation of the error in dependence of radial velocity shift, spectral resolution, and target line-profile function by use of high-resolution atmospheric transmission modeling, which has to be solved for the individual case.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

MiniCarb: a passive, occultation-viewing, 6U CubeSat for observations of CO 2 , CH 4 , and H 2 O

In this report we present the final design, environmental testing, and launch history of MiniCarb, a 6U CubeSat developed through a partnership between NASA Goddard Space Flight Center and Lawrence Livermore National Laboratory. MiniCarb’s science payload, developed at Goddard, was an occultation-viewing, passive laser heterodyne radiometer for observing methane, carbon dioxide, and water vapor in Earth’s atmosphere at ~1.6 µm s -1 . MiniCarb’s satellite, developed at Livermore, implemented their CubeSat Next Generation Bus plug-and-play architecture to produce a modular platform that could be tailored to a range of science payloads. Following the launch on 5 December 2019, MiniCarb traveled to the International Space Station and was set into orbit on 1 February 2020 via Northrop Grumman’s Cygnus capsule which deployed MiniCarb with tipoff rotation of about 20° s (significantly higher than the typical rate of 3° s -1 from prior CubeSats), from which the attitude control system was unable to recover resulting in a loss of power. In spite of this early failure, MiniCarb had many successes including rigorous environmental testing, successful deployment of its solar panels, and a successful test of the radio and communication through the Iridium network. This prior work and enticing cost (approximately $\$2$ M for the satellite and $\$$250 K for the payload) makes MiniCarb an ideal candidate for a low-cost and rapid rebuild as a single orbiter or constellation to globally observe key greenhouse gases.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

A Dynamic Trajectory Fit to Multisensor Fireball Observations

Meteorites with known orbital origins are key to our understanding of solar system formation and the source of life on Earth. Fireball networks have been developed globally in a unified effort to record and ultimately retrieve these cosmic samples. However, the accuracy of the determined orbit and the likelihood of meteorite recovery depend directly on the accuracy of the chosen meteoroid triangulation method. There are three leading techniques for meteoroid triangulation discussed in the literature: the method of planes, the straight-line least-squares method, and the multiparameter fit method. Here we describe an alternative method to meteoroid triangulation, called the dynamic trajectory fit. This approach uses the meteoroid’s 3D dynamic equations of motion to fit a realistic trajectory directly to multisensor line-of-sight observations. This method has the ability to resolve fragmentation events, fit systematic observatory timing offsets, and determine mass estimates of the meteoroid along its observable trajectory. Through a comprehensive Monte Carlo analysis of over 100,000 trajectory simulations, we find this new method to more accurately estimate meteoroid trajectories of slow entry events (<25 km s{sup −1}) and events observed from low convergence angles (<10°) compared to existing meteoroid triangulation techniques. Additionally, we triangulate an observed fireball event with visible fragmentation using the various triangulation methods to show that the proposed dynamic trajectory fit implementing fragmentation to best match the captured multisensor line-of-sight data.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Projected Seismic Activity at the Tiger Stripe Fractures on Enceladus, Saturn, From an Analog Study of Tidally Modulated Icequakes Within the Ross Ice Shelf, Antarctica

Abstract Dissipation of tidal energy is expected to generate seismicity on icy‐ocean worlds; however, the distribution and timing of this seismic activity throughout an orbital cycle is not known. We used new observations from an icy‐ocean‐world analog environment on Earth to examine the relationship between tidally driven tensile stress and seismic activity within an ice shell. We investigated a pair of rifts within Antarctica's Ross Ice Shelf which are tidally stressed in a manner analogous to the orbital cycle of tidal stress experienced by Enceladus' Tiger Stripe Fractures. We found that seismic activity at the Antarctic rifts is sensitive to both the amplitude and the rate of tensile stress across the rifts. We combined these findings with calculated stress values along Enceladus' Tiger Stripe Fractures to predict seismic‐activity levels expected along the ice‐shell fractures. We predict a peak in seismicity along the four Tiger Stripe Fractures when Enceladus is 90°–120° past pericenter in its orbit around Saturn, at which point tensile stresses would reach ∼2/3 of their maximum value. We also used the magnitude distribution of icequakes along Antarctic rifts to investigate implications for the likely size of stick‐slip rupture patches along icy faults on Enceladus. Our findings predict that the Tiger Stripe Fractures should produce sustained, low‐magnitude seismic events that involve rupture along discrete portions of each fracture's total length. We predict that seismicity would fall to 50% of peak levels when stresses across the Tiger Stripe Fractures are dominantly compressional.

Olsen, Kira G.↗
DOE OSTI2026

Constraining the Hydration of Clay Minerals and Abundances of Amorphous Phases in Gale Crater, Mars

Both water and organic matter are required for the development and persistence of life. Phyllosilicates (clay minerals) have high surface areas that easily sorb water and organic matter. The Curiosity rover has investigated several hundred meters of stratigraphy in Gale crater, including where clays were detected from orbit. Previous results have suggested that subsurface hydration is greatest in units with the most abundant clays, suggesting that these minerals may be hydrated. Organics have also been found throughout Gale crater. Smectites are the most common and abundant phyllosilicates in Gale crater samples and can expand and sorb water and organics in interlayer sites. The most common organic sorption processes on Earth typically involve water or hydroxyl, so hydrated phyllosilicates are good candidates for organic preservation. Using newly derived subsurface hydration results with previously published mineralogy and geochemistry, we derived modeled constraints on the abundances of hydrated amorphous phases, “excess” water, and “excess” cations. These “excess” phases are not accounted for by published crystalline phase abundances or by amorphous phases constrained here. We found correlations between smectites and both “excess” water and “excess” cation abundances, indicating that smectites in Gale crater are hydrated and that cation bridging could be a mechanism for sorption of organics. Our results also show the persistence of amorphous sulfates, opal-A, and volcanic or impact glass, which indicate low water-rock interactions. Increased abundances of sulfates and glass in stratigraphically higher samples may indicate lower water availability and environmental aridification during the time these units were being deposited.

58 GEOSCIENCES↗
DOE OSTI2023

Making a Superbolt: Reconciling Observations of the Optically Brightest Lightning on Earth From Different Satellites

We previously documented geographic distributions of the optically brightest lightning on Earth—known as “superbolts”—using two space-based instruments: the photodiode detector (PDD) on the Fast On-orbit Recording of Transient Events (FORTE) satellite and the Geostationary Lightning Mapper (GLM) on NOAA's Geostationary Operational Environmental Satellites. In this study, we further examine the superbolts identified by the PDD and GLM to reconcile the differences between their geographic distributions. We find that both the physical extent of the parent flash and the development speed of its leaders are important for making a superbolt. The oceanic PDD superbolts tend to occur early in flashes that rapidly expand laterally into long horizontal “megaflashes.” The top GLM superbolts occur over land at later times in particularly large megaflashes. These land-based flashes grow more slowly until they extend over multiple hundreds of kilometers. The FORTE PDD missed these delayed superbolts due to limitations in its triggering. Coincident Tropical Rainfall Measuring Mission measurements show that the warm season megaflash superbolts detected by Lightning Imaging Sensor/GLM and wintertime oceanic superbolts observed by the PDD occur in otherwise similar thunderstorm environments. Both are marked by: low storm heights (<10 km), widespread precipitation near the surface, small infrared brightness temperature gradients, and low flash rates. We suggest that the vertically compact, stratiform nature of these clouds provides favorable conditions for superbolt production.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Emergent quasi-one-dimensional antiferromagnetism in the distorted kagome magnet CePtPb

CePtPb hosts a distorted kagome lattice of Ce 3+ ions, providing a clean platform to investigate how reduced local symmetry and strong spin-orbit coupling reshape frustrated magnetism. Magnetization, specific heat, and magnetocaloric effect measurements, combined with a symmetry analysis of the single-ion anisotropy, demonstrate that the local 𝑚⁢2⁢𝑚 site symmetry selects a nearly Ising-like Kramers doublet with easy axes lying within the 𝑎⁢𝑏 plane. This results in three distinct in-plane Ising directions and an overall easy-plane anisotropy. The low-energy magnetic response is well captured by a three-sublattice Ising model, which quantitatively reproduces the saturation magnetization for arbitrary in-plane field orientations, including $[110]$ and $[1\bar{⁢1}⁢0]$, as well as the ratio of the field-induced critical fields. For 𝐵∥$[110]$, the phase diagram exhibits two quantum critical points at 𝐵 c⁢1 = 0.25T and 𝐵 c⁢2 = 0.55T, arising from the sequential polarization of the three Ising sublattices. In conclusion, these results reveal that the system develops quasi-one-dimensional spin chains along the 𝑐 axis, emerging from the nominally three-dimensional crystal structure composed of stacked kagome layers, and illustrate how reduced local symmetry can drive effective dimensional reduction in rare-earth Ising magnets.

Li, Fangli [Southern University of Science and Tec↗
DOE OSTI2021

Detection Limits of Low-mass, Long-period Exoplanets Using Gaussian Processes Applied to HARPS-N Solar Radial Velocities

Radial velocity (RV) searches for Earth-mass exoplanets in the habitable zone around Sun-like stars are limited by the effects of stellar variability on the host star. In particular, suppression of convective blueshift and brightness inhomogeneities due to photospheric faculae/plage and starspots are the dominant contribution to the variability of such stellar RVs. Gaussian process (GP) regression is a powerful tool for statistically modeling these quasi-periodic variations. We investigate the limits of this technique using 800 days of RVs from the solar telescope on the High Accuracy Radial velocity Planet Searcher for the Northern hemisphere (HARPS-N) spectrograph. These data provide a well-sampled time series of stellar RV variations. Into this data set, we inject Keplerian signals with periods between 100 and 500 days and amplitudes between 0.6 and 2.4 m s{sup −1}. We use GP regression to fit the resulting RVs and determine the statistical significance of recovered periods and amplitudes. We then generate synthetic RVs with the same covariance properties as the solar data to determine a lower bound on the observational baseline necessary to detect low-mass planets in Venus-like orbits around a Sun-like star. Our simulations show that discovering planets with a larger mass (∼0.5 m s{sup −1}) using current-generation spectrographs and GP regression will require more than 12 yr of densely sampled RV observations. Furthermore, even with a perfect model of stellar variability, discovering a true exo-Venus (∼0.1 m s{sup −1}) with current instruments would take over 15 yr. Therefore, next-generation spectrographs and better models of stellar variability are required for detection of such planets.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Charge order and superconductivity in a two-band model for infinite-layer nickelates

The recent discovery of superconductivity in infinite-layer nickelates has drawn considerable attention; however, a consensus on the fundamental building blocks and common ingredients necessary to understand and describe their ground states and emergent properties is lacking. A series of experimental and theoretical studies have suggested that an effective two-band Hubbard model with Ni 3d x 2 -y 2 and rare-earth (R) 5d character may describe the low-energy physics. In this report we study the ground state properties of this two-band model on four-leg cylinders using the density-matrix renormalization group (DMRG) technique to better grasp whether such a simple model can embody the essential physics. A key difference compared to single-band Hubbard materials is that the system is self-doped: even at overall half-filling, the R-band acts as an electron reservoir, hole-doping the Ni-layer and fundamentally altering the physics expected from an undoped antiferromagnet. On the four-leg cylinder, the ground state is consistent with a Luttinger liquid, with anti-phase modulations of the charge density in the Ni- and R-layers having corresponding wavevectors that lock together. Light hole doping away from 1/2 filling releases the locking between the Ni and the R charge modulations, as the electron density in the R-band decreases and eventually becomes exhausted at a hole doping concentration that depends sensitively on the effective splitting between the Ni and the R orbitals. The ground state of the doped system is consistent with a Luther-Emery liquid, possessing quasi-long-range superconducting correlations in the Ni layer, similar to the single-band Hubbard model. Our results are consistent with experimental observations and may help to reveal the microscopic mechanism for pairing and other emergent properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Electronic structure and photophysics of a supermolecular iron complex having a long MLCT-state lifetime and panchromatic absorption

Exploiting earth-abundant iron-based metal complexes as high-performance photosensitizers demands long-lived electronically excited metal-to-ligand charge-transfer (MLCT) states, but these species suffer typically from femtosecond timescale charge-transfer (CT)-state quenching by low-lying nonreactive metal-centered (MC) states. Here, we engineer supermolecular Fe(II) chromophores based on the bis(tridentate-ligand)metal(II)-ethyne-(porphinato)zinc(II) conjugated framework, previously shown to give rise to highly delocalized low-lying 3 MLCT states for other Group VIII metal (Ru, Os) complexes. Electronic spectral, potentiometric, and ultrafast pump–probe transient dynamical data demonstrate that a combination of a strong σ-donating tridentate ligand and a (porphinato)zinc(II) moiety with low-lying π*-energy levels, sufficiently destabilize MC states and stabilize supermolecular MLCT states to realize Fe(II) complexes that express 3 MLCT state photophysics reminiscent of their heavy-metal analogs. The resulting Fe(II) chromophore archetype, FeNHCPZn, features a highly polarized CT state having a profoundly extended 3MLCT lifetime (160 ps), 3 MLCT phosphorescence, and ambient environment stability. Density functional and domain-based local pair natural orbital coupled cluster [DLPNO-CCSD(T)] theory reveal triplet-state wavefunction spatial distributions consistent with electronic spectroscopic and excited-state dynamical data, further underscoring the dramatic Fe metal-to-extended ligand CT character of electronically excited FeNHCPZn. This design further prompts intense panchromatic absorptivity via redistributing high-energy absorptive oscillator strength throughout the visible spectral domain, while maintaining a substantial excited-state oxidation potential for wide-ranging photochemistry––highlighted by the ability of FeNHCPZn to photoinject charges into a SnO 2 /FTO electrode in a dye-sensitized solar cell (DSSC) architecture. Concepts enumerated herein afford opportunities for replacing traditional rare-metal–based emitters for solar-energy conversion and photoluminescence applications.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Cyclometallated Co(III) Complexes with Lowest-Energy Charge Transfer Excited States Accessible with Visible Light

The Co(III) complexes, cis-[Co(ppy) 2 (L)]PF 6 , where ppy = 2-phenylpyridine and L = bpy (2,2′-bipyridine; 1), phen (1,10-phenanthroline; 2), and DAP (1,12-diazaperylene; 3), are reported and their photophysical properties were investigated to evaluate their potential as sensitizers for applications that include solar energy conversion schemes and photoredox catalysis. Calculations show that cyclometallation in the cis-[Co(ppy) 2 (L)]PF 6 series affords strong Co(dπ)/ppy(π) orbital interactions that result in a Co/ppy(π*) highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) localized on the diimine ligand, L(π*). Complexes 1–3 exhibit relatively invariant oxidation potentials, whereas the reduction event is dependent on the identity of the diimine ligand, L, consistent with the theoretical predictions. For 3 a broad Co/ppy(π*) → L(π*) metal/ligand-to-ligand charge transfer (ML-LCT) absorption band is observed in CH 3 CN with a maxima at 507 nm, extending beyond 600 nm. Upon excitation of the 1ML-LCT transition, transient absorption features consistent with the population of a 3 ML-LCT excited state with lifetimes, τ, of 3.0 ps, 4.6 and 42 ps for 1, 2 and 3 in CH 3 CN respectively are observed. Upon irradiation with 505 nm, 3 is able to reduce methyl viologen (MV 2+ ), an electron acceptor commonly in photocatalytic schemes. Here, to our knowledge, 3 represents the first heteroleptic molecular Co(III) complex that combines cyclometallation with a diimine ligand with lowest-lying metal-to-ligand charge transfer excited states able to undergo photoinduced charge transfer with low-energy green light. As such, the structural design of 3 represents an important step toward d6 photosensitizers based on earth abundant metals.

Energy↗