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At least 1,459 records · Page 81

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NASA NTRS1994

Software for continuum modeling of controls-structures interactions

It is clear that computer software is needed to assist in the generation of the equations of motion for complex, flexible spacecraft. Daniel Poelaert of ESTEC has developed the software DISTEL with which he has modeled the structural dynamics for different satellites. He is interested in expanding the capabilities of DISTEL to include structural damping and control systems. Unfortunately, the software has not been released. The author has developed similar software, PDEMOD, which has been used to model the Spacecraft control Laboratory Experiment (SCOLE), the Solar Array Flight Experiment (SAFE), the Mini-MAST truss, and the LACE satellite. PDEMOD has been used also for optimal parameter estimation and integrated control-structures design. PDEMOD is also being extended to include structural damping and control systems which are imbedded into the same equations for the structural dynamics. This paper will address the formulation of the equations for the structural dynamics of spacecraft structures which are constructed of a 3-dimensional arrangement of rigid bodies and flexible beam elements. Control system dynamics are imbedded into the same equations so that model order reduction approximations are not necessary. The input data consists of the physical data of the elements and the topological information describing how the elements are connected. PDEMOD accomplishes the following: (1) automatically assembles the equations of motion for the entire structural model; (2) calculates the modal frequencies; (3) calculates the mode shapes; (4) generates perspective views of the mode shapes; and (5) forms selected transfer functions. The software PDEMOD continues to be developed to provide additional features to assist in analyzing and synthesizing control and structural systems for flexible spacecraft.

Taylor, Lawrence W., Jr.↗

NASA NTRS1994

Actuator Feasibility Study for Active Control of Ducted Axial Fan Noise

A feasibility study was performed to investigate actuator technology which is relevant for a particular application of active noise control for gas turbine stator vanes. This study investigated many different classes of actuators and ranked them on the order of applicability. The most difficult requirements the actuators had to meet were high frequency response, large amplitude deflections, and a thin profile. Based on this assessment, piezoelectric type actuators were selected as the most appropriate actuator class. Specifically, Rainbows (a new class of high performance piezoelectric actuators), and unimorphs (a ceramic/metal composite) appeared best suited to the requirements. A benchtop experimental study was conducted. The performance of a variety of different actuators was examined, including high polymer films, flextensional actuators, miniature speakers, unimorphs, and Rainbows. The displacement/frequency response and phase characteristics of the actuators were measured. Physical limitations of actuator operation were also examined. This report includes the first known, high displacement, dynamic data obtained for Rainbow actuators. A new "hard" ceramic Rainbow actuator which does not appear to be limited in operation by self heating as "soft" ceramic Rainbows was designed, constructed and tested. The study concludes that a suitable actuator for active noise control in gas turbine engines can be achieved with state of the art materials and processing.

Simonich, John C.↗

NASA NTRS2012

Broadband Liner Optimization for the Source Diagnostic Test Fan

The broadband component of fan noise has grown in relevance with the utilization of increased bypass ratio and advanced fan designs. Thus, while the attenuation of fan tones remains paramount, the ability to simultaneously reduce broadband fan noise levels has become more appealing. This paper describes a broadband acoustic liner optimization study for the scale model Source Diagnostic Test fan. Specifically, in-duct attenuation predictions with a statistical fan source model are used to obtain optimum impedance spectra over a number of flow conditions for three liner locations in the bypass duct. The predicted optimum impedance information is then used with acoustic liner modeling tools to design liners aimed at producing impedance spectra that most closely match the predicted optimum values. Design selection is based on an acceptance criterion that provides the ability to apply increased weighting to specific frequencies and/or operating conditions. Typical tonal liner designs targeting single frequencies at one operating condition are first produced to provide baseline performance information. These are followed by multiple broadband design approaches culminating in a broadband liner targeting the full range of frequencies and operating conditions. The broadband liner is found to satisfy the optimum impedance objectives much better than the tonal liner designs. In addition, the broadband liner is found to provide better attenuation than the tonal designs over the full range of frequencies and operating conditions considered. Thus, the current study successfully establishes a process for the initial design and evaluation of novel broadband liner concepts for complex engine configurations.

Nark, Douglas M.↗

NASA NTRS2014

Improved Broadband Liner Optimization Applied to the Advanced Noise Control Fan

The broadband component of fan noise has grown in relevance with the utilization of increased bypass ratio and advanced fan designs. Thus, while the attenuation of fan tones remains paramount, the ability to simultaneously reduce broadband fan noise levels has become more desirable. This paper describes improvements to a previously established broadband acoustic liner optimization process using the Advanced Noise Control Fan rig as a demonstrator. Specifically, in-duct attenuation predictions with a statistical source model are used to obtain optimum impedance spectra over the conditions of interest. The predicted optimum impedance information is then used with acoustic liner modeling tools to design liners aimed at producing impedance spectra that most closely match the predicted optimum values. Design selection is based on an acceptance criterion that provides the ability to apply increased weighting to specific frequencies and/or operating conditions. Constant-depth, double-degree of freedom and variable-depth, multi-degree of freedom designs are carried through design, fabrication, and testing to validate the efficacy of the design process. Results illustrate the value of the design process in concurrently evaluating the relative costs/benefits of these liner designs. This study also provides an application for demonstrating the integrated use of duct acoustic propagation/radiation and liner modeling tools in the design and evaluation of novel broadband liner concepts for complex engine configurations.

Nark, Douglas M.↗

NASA NTRS2016

Statistically Based Approach to Broadband Liner Design and Assessment

A broadband liner design optimization includes utilizing in-duct attenuation predictions with a statistical fan source model to obtain optimum impedance spectra over a number of flow conditions for one or more liner locations in a bypass duct. The predicted optimum impedance information is then used with acoustic liner modeling tools to design liners having impedance spectra that most closely match the predicted optimum values. Design selection is based on an acceptance criterion that provides the ability to apply increasing weighting to specific frequencies and/or operating conditions. One or more broadband design approaches are utilized to produce a broadband liner that targets a full range of frequencies and operating conditions.

Nark, Douglas M.↗

NASA NTRS2021

Assessing within-Field Corn and Soybean Yield Variability from WorldView-3, Planet, Sentinel-2, and Landsat 8 Satellite Imagery

Crop yield monitoring is an important component in agricultural assessment. Multispectral remote sensing instruments onboard space-borne platforms such as Advanced Very High Resolution Radiometer (AVHRR), Moderate Resolution Imaging Spectroradiometer (MODIS), and Visible Infrared Imaging Radiometer Suite (VIIRS) have shown to be useful for efficiently generating timely and synoptic information on the yield status of crops across regional levels. However, the coarse spatial resolution data inherent to these sensors provides little utility at the management level. Recent satellite imagery collection advances toward finer spatial resolution (down to 1 m) alongside increased observational cadence (near daily) implies information on crops obtainable at field and within-field scales to support farming needs is now possible. To test this premise, we focus on assessing the efficiency of multiple satellite sensors, namely WorldView-3, Planet/Dove-Classic, Sentinel-2, and Landsat 8 (through Harmonized Landsat Sentinel-2 (HLS)), and investigate their spatial, spectral (surface reflectance (SR) and vegetation indices (VIs)), and temporal characteristics to estimate corn and soybean yields at sub-field scales within study sites in the US state of Iowa. Precision yield data as referenced to combine harvesters’ GPS systems were used for validation. We show that imagery spatial resolution of 3 m is critical to explaining 100% of the within-field yield variability for corn and soybean. Our simulation results show that moving to coarser resolution data of 10 m, 20 m, and 30 m reduced the explained variability to 86%, 72%, and 59%, respectively. We show that the most important spectral bands explaining yield variability were green (0.560 µm), red-edge (0.726 µm), and near-infrared (NIR - 0.865 µm). Furthermore, the high temporal frequency of Planet and a combination of Sentinel-2/Landsat 8 (HLS) data allowed for optimal date selection for yield map generation. Overall, we observed mixed performance of satellite-derived models with the coefficient of determination (R^2) varying from 0.21 to 0.88 (averaging 0.56) for the 30 m HLS and from 0.09 to 0.77 (averaging 0.30) for 3 m Planet. R^2 was lower for fields with higher yields, suggesting saturation of the satellite-collected reflectance features in those cases. Therefore, other biophysical variables, such as soil moisture and evapotranspiration, at similar fine spatial resolutions are likely needed alongside the optical imagery to fully explain the yields.

agriculture; yield; within-field; corn; soybean; r↗

DOE OSTI2020

History of Ultrasonic Inspection of High-Level Waste Tanks at SRS - 20220

The Liquid Waste Disposition Projects (LWDP) Structural Authority and Inspection Engineering Support Group has teamed with the Materials Science and Technology Non-destructive Evaluation Group of Savannah River National Laboratory (SRNL) to implement a comprehensive In-Service Inspection (ISI) program for the High-Level Waste (HLW) tanks in the sites tank farms. The purpose of this program is to demonstrate the structural and leak integrity of the tanks to maintain the function of waste containment throughout the desired service life. Four types of waste tanks were constructed at Savannah River Site (SRS) from 1951 thru 1981 to store radioactive nuclear waste from the separations process. The Type I, II and III are carbon steel cylindrical tanks with varying degrees of access to the side walls and very limited access to the tank bottom. The tanks contain 750,000 to 1.3 million gallons of waste and are buried or backfilled with soil. The tanks are 75'-85' in diameter and 24'-33' from tank bottom to the tank roof. Inspection of the HLW tanks is made difficult by radiation, contamination, and small access openings. Through the years these challenges have been overcome by progressive improvements to programs and equipment resulting in the sophisticated wall crawler Ultrasonic Testing (UT) technology of today. A formal inspection program was developed and put in service in 1972. UT thickness measurements were first made in 1967 and 1969 of selected waste tanks using an analog-type instrument to measure the thickness of the carbon steel walls. Routine inspections for thinning were performed from 1972-1985 and then discontinued because no thinning had been observed and this technique could not detect pitting or cracking. UT inspections resumed in 1994 using a sophisticated robotic wall crawler with UT technology capable of detecting thinning, cracking and pitting. The current program focuses on the newer Type III tanks that are used primarily for storage. The program was upgraded in 2003 to include selected regions of the tank wall, secondary wall and annulus floor on a 7 to 10-year frequency. The facility is currently in its third cycle of tank inspections. Thus far, there have been no reportable indications of service induced degradation. This result provides assurance that the chemistry control program has been effective at mitigating corrosion and that the tanks remain structurally sound even after more than 40 years of service. This paper will present the UT technology first used at SRS and the evolution to the current systems and their capabilities. Additionally, plans for equipment upgrades that will improve the extent of inspection will be discussed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Beam Dynamics Challenges in the Muon g-2 Experiment

The muon&s;s anomalous magnetic moment $a_{\mu}$ has hinted at physics beyond the standard model for nearly 20 years. The Muon $g-2$ experiment at Fermilab aims to measure $a_{\mu}$ to 140 parts per billion (ppb) precision. The 460 ppb result from its first data run (Run-1), released in 2021, agreed with the previous 2006 Brookhaven Muon $g-2$ result. The experimental average stands in tension with the standard model theory $a_{\mu}$ prediction by $4.2 \sigma$. The result of Run-2/3 data analysis is set be released in summer 2023, and will improve on the Run-1 precision by a factor of two. With the data collected in all six runs, the experiment is on track to produce a 140 ppb measurement of $a_{\mu}$. If the experiment and theory central values are both unchanged, the tension would exceed $5 \sigma$. The measurement is accomplished by injecting muons into a magnetic storage ring and precisely measuring two observable frequencies: $\omega_a$, the muons&s; anomalous precession frequency, and $\tilde{\omega}&s;_p$, the precession frequency of protons which determines the magnetic field strength experienced by the muons. This thesis presents a selection of muon beam dynamics effects which are critical for reaching the experiment precision goal. A system of detectors assists with the challenging beam injection into the storage ring, and a measurement of the injected beam provides input for simulating the stored beam dynamics. A new method is introduced to reduce a critical systemic caused by time dependence in the stored beam momentum, enabled by a detector which directly profiles the stored beam. Finally the analysis of $\tilde{\omega}&s;_p$, the muon-weighted magnetic field, for the Run-2/3 result is presented. Systematics of $\tilde{\omega}&s;_p$ due to beam effects are evaluated in detail, and shown to be sub-dominant.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2017

Hydroisomerization of n-hexadecane: remarkable selectivity of mesoporous silica post-synthetically modified with aluminum

As the impact of acids on catalytically driven chemical transformations is tremendous, fundamental understanding of catalytically relevant factors is essential for the design of more efficient solid acid catalysts. In this work, we employed a post-synthetic doping method to synthesize a highly selective hydroisomerization catalyst and to demonstrate the effect of acid strength and density, catalyst microstructure, and platinum nanoparticle size on the reaction rate and selectivity. Aluminum doped mesoporous silica catalyzed gas-phase n-hexadecane isomerization with remarkably high selectivity to monobranched isomers (~95%), producing a substantially higher amount of isomers than traditional zeolite catalysts. Mildly acidic sites generated by post-synthetic aluminum grafting were found to be the main reason for its high selectivity. The flexibility of the post-synthetic doping method enabled us to systematically explore the effect of the acid site density on the reaction rate and selectivity, which has been extremely difficult to achieve with zeolite catalysts. We found that a higher density of Brønsted acid sites leads to higher cracking of n-hexadecane presumably due to an increased surface residence time. Furthermore, regardless of pore size and microstructure, hydroisomerization turnover frequency linearly increased as a function of Brønsted acid site density. In addition to strength and density of acid sites, platinum nanoparticle size affected catalytic activity and selectivity. The smallest platinum nanoparticles produced the most effective bifunctional catalyst presumably because of higher percolation into aluminum doped mesoporous silica, generating more 'intimate' metallic and acidic sites. Finally, the aluminum doped silica catalyst was shown to retain its remarkable selectivity towards isomers even at increased reaction conversions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Belowground Carbohydrate Reserves of Mature Southern Pines Reflect Seedling Strategy to Evolutionary History of Disturbance

Carbohydrate reserves provide advantages for mature trees experiencing frequent disturbances; however, it is unclear if selective pressures operate on this characteristic at the seedling or mature life history stage. We hypothesized that natural selection has favored carbohydrate reserves in species that have an evolutionary history of frequent disturbance and tested this using three southern pine species that have evolved across a continuum of fire frequencies. Longleaf pine (Pinus palustris) roots exhibited higher maximum starch concentrations than slash (P. elliottii) and loblolly (P. taeda), which were similar. Longleaf also relied on starch reserves in roots more than slash or loblolly, depleting 64, 41, and 23 mg g -1 of starch, respectively, between seasonal maximum and minimum, which represented 52%, 45%, and 26% of reserves, respectively. Starch reserves in stems did not differ among species or exhibit temporal dynamics. Our results suggest that an evolutionary history of disturbance partly explains patterns of carbohydrate reserves observed in southern pines. However, similarities between slash and loblolly indicate that carbohydrate reserves do not strictly follow the continuum of disturbance frequencies among southern pine, but rather reflect the different seedling strategies exhibited by longleaf compared to those shared by slash and loblolly. We propose that the increased carbohydrate reserves in mature longleaf may simply be a relic of selective pressures imposed at the juvenile stage that are maintained through development, thus allowing mature trees to be more resilient and to recover from chronic disturbances such as frequent fire.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1974

Frequency standard stability for Doppler measurements on-board the shuttle

The short and long term stability characteristics of crystal and atomic standards are described. Emphasis is placed on crystal oscillators because of the selection which was made for the shuttle baseline and the complexities which are introduced by the shuttle environment. Attention is given, first, to the definitions of stability and the application of these definitions to the shuttle system and its mission. Data from time domain measurements are used to illustrate the definitions. Results of a literature survey to determine environmental effects on frequency reference sources are then presented. Finally, methods of standard frequency dissemination over radio frequency carriers are noted as a possible means of measuring absolute accuracy and long term stability characteristics during on one way Doppler equipment.

Harton, P. L.↗

DOE OSTI2020

The Frequency of Sex: Population Genomics Reveals Differences in Recombination and Population Structure of the Aflatoxin-Producing Fungus Aspergillus flavus

The apparent rarity of sex in many fungal species has raised questions about how much sex is needed to purge deleterious mutations and how differences in frequency of sex impact fungal evolution. We sought to determine how differences in the extent of recombination between populations of Aspergillus flavus impact the evolution of genes associated with the synthesis of aflatoxin, a notoriously potent carcinogen. We sequenced the genomes of, and quantified aflatoxin production in, 94 isolates of A. flavus sampled from seven states in eastern and central latitudinal transects of the United States. The overall population is subdivided into three genetically differentiated populations (A, B, and C) that differ greatly in their extent of recombination, diversity, and aflatoxin-producing ability. Estimates of the number of recombination events and linkage disequilibrium decay suggest relatively frequent sex only in population A. Population B is sympatric with population A but produces significantly less aflatoxin and is the only population where the inability of nonaflatoxigenic isolates to produce aflatoxin was explained by multiple gene deletions. Population expansion evident in population B suggests a recent introduction or range expansion. Population C is largely nonaflatoxigenic and restricted mainly to northern sampling locations through restricted migration and/or selection. Despite differences in the number and type of mutations in the aflatoxin gene cluster, codon optimization and site frequency differences in synonymous and nonsynonymous mutations suggest that low levels of recombination in some A. flavus populations are sufficient to purge deleterious mutations.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2001

Effect of Selectively Etched Ferroelectric Thin-Film Layer on the Performance of a Tunable Bandpass Filter

The main purpose of this work is to study the effect of a selectively etched ferroelectric thin film layer on the performance of an electrically tunable filter. An X-band tunable filter was designed, fabricated and tested on a selectively etched Barium Strontium Titanate (BSTO) ferroelectric thin film layer. Tunable filters with varying lengths of BSTO thin-film in the input and output coupling gaps were modeled, as well as experimentally tested. Experimental results showed that filters with coupling gaps partially filled with BSTO maintained frequency tunability and improved the insertion loss by approx. 2dB. To the best of our knowledge, these results represent the first experimental demonstration of the advantages of selective etching in the performance of thin film ferroelectric-based tunable microwave components.

Subramanyam, Guru↗

NASA NTRS2014

Communications Technology Assessment for the Unmanned Aircraft System (UAS) Control and Non-Payload Communications (CNPC) Link

The National Aeronautics and Space Administration (NASA) Glenn Research Center (GRC) is performing communications systems research for the Unmanned Aircraft System (UAS) in the National Airspace System (NAS) Project. One of the goals of the communications element is to select and test a communications technology for the UAS Control and Non-Payload Communications (CNPC) link. The GRC UAS Modeling and Simulation (M/S) Sub Team will evaluate the performance of several potential technologies for the CNPC link through detailed software simulations. In parallel, an industry partner will implement a technology in hardware to be used for flight testing. The task necessitated a technical assessment of existing Radio Frequency (RF) communications technologies to identify the best candidate systems for use as the UAS CNPC link. The assessment provides a basis for selecting the technologies for the M/S effort and the hardware radio design. The process developed for the technical assessments for the Future Communications Study1 (FCS) was used as an initial starting point for this assessment. The FCS is a joint Federal Aviation Administration (FAA) and Eurocontrol study on technologies for use as a future aeronautical communications link. The FCS technology assessment process methodology can be applied to the UAS CNPC link; however the findings of the FCS are not directly applicable because of different requirements between a CNPC link and a general aeronautical data link. Additional technologies were added to the potential technologies list from the State of the Art Unmanned Aircraft System Communication Assessment developed by NASA GRC2. This document investigates the state of the art of communications as related to UAS. A portion of the document examines potential communications systems for a UAS communication architecture. Like the FCS, the state of the art assessment surveyed existing communications technologies. It did not, however, perform a detailed assessment of the technology necessary to recommend a technology for the UAS CNPC link. The technical assessment process, as shown in Figure 1, consists of the following steps. First, candidate RF communications technologies are identified. An initial review of each of these technologies is then performed to determine if the technology appears to be a good candidate and requires further review. Any technology that can be shown to be inadequate at that point is removed from consideration to allow for more detailed analysis of the remaining technologies. Criteria for the detailed assessments are defined and a scoring methodology is devised. This is followed by the detailed review and scoring of each technology. The least favorable technologies are removed during the process until only the few best candidates remain.

Aircraft Command and Control↗

DOE OSTI2019

Parallel programming of an ionic floating-gate memory array for scalable neuromorphic computing

Neuromorphic computers could overcome efficiency bottlenecks inherent to conventional computing through parallel programming and readout of artificial neural network weights in a crossbar memory array. However, selective and linear weight updates and <10-nanoampere read currents are required for learning that surpasses conventional computing efficiency. We introduce an ionic floating-gate memory array based on a polymer redox transistor connected to a conductive-bridge memory (CBM). Selective and linear programming of a redox transistor array is executed in parallel by overcoming the bridging threshold voltage of the CBMs. Synaptic weight readout with currents <10 nanoamperes is achieved by diluting the conductive polymer with an insulator to decrease the conductance. The redox transistors endure >1 billion write-read operations and support >1-megahertz write-read frequencies.

bio-inspired, energy storage (including batteries ↗

NASA NTRS2013

Multimode Directional Coupler for Utilization of Harmonic Frequencies from TWTAs

A novel waveguide multimode directional coupler (MDC) intended for the measurement and potential utilization of the second and higher order harmonic frequencies from high-power traveling wave tube amplifiers (TWTAs) has been successfully designed, fabricated, and tested. The design is based on the characteristic multiple propagation modes of the electrical and magnetic field components of electromagnetic waves in a rectangular waveguide. The purpose was to create a rugged, easily constructed, more efficient waveguide- based MDC for extraction and exploitation of the second harmonic signal from the RF output of high-power TWTs used for space communications. The application would be a satellitebased beacon source needed for Qband and V/W-band atmospheric propagation studies. The MDC could function as a CW narrow-band source or as a wideband source for study of atmospheric group delay effects on highdata- rate links. The MDC is fabricated from two sections of waveguide - a primary one for the fundamental frequency and a secondary waveguide for the second harmonic - that are joined together such that the second harmonic higher order modes are selectively coupled via precision- machined slots for propagation in the secondary waveguide. In the TWTA output waveguide port, both the fundamental and the second harmonic signals are present. These signals propagate in the output waveguide as the dominant and higher order modes, respectively. By including an appropriate mode selective waveguide directional coupler, such as the MDC presented here at the output of the TWTA, the power at the second harmonic can be sampled and amplified to the power level needed for atmospheric propagation studies. The important conclusions from the preliminary test results for the multimode directional coupler are: (1) the second harmonic (Ka-band) can be measured and effectively separated from the fundamental (Ku-band) with no coupling of the latter, (2) power losses in the fundamental frequency are negligible, and (3) the power level of the extracted second harmonic is sufficient for further amplification to power levels needed for practical applications. It was also demonstrated that third order and potentially higher order harmonics are measurable with this device. The design is frequency agnostic, and with the appropriate choice of waveguides, is easily scaled to higher frequency TWTs. The MDC has the same function but with a number of important advantages over the conventional diplexer.

Simmons, Rainee N.↗

NASA NTRS1994

A Spectral Atlas of the Nu(sub 12) Fundamental of (13)C(12)CH6 in the 12 Micron Region

The recent discovery of the minor isotopomer of ethane, (13)C(12)CH6, in the planetary atmospheres of Jupiter and Neptune, added ethane to the molecules which can be used to determine isotopic (12)C(12)C ratios for the jovian planets. The increased spectral resolution and coverage of the IR and far-IR instruments to be carried on the Cassini mission to Saturn and Titan may enable the detection of the minor isotopomer. Accurate frequency and cross-section measurements of the nu(sub 12) fundamental under controlled laboratory condition are important to interpret current and future planetary spectra. High resolution spectra of the minor isotopomer (13)C(12)CH6 have been recorded in the 12.2 micron region using the Kitt Peak Fourier Transform (FTS) and the Goddard Tunable Diode Laser spectrometer (TDL). In a global fit to 19 molecular constants in a symmetric top Hamiltonian, transition frequencies of the nu(sub 12) fundamental ranging up to J=35 and K=20 have been determined with a standard deviation of less than 0.0005 cm(exp -1). From selected line intensity measurements, a vibrational dipole moment for the nu(sub 12) fundamental has been derived. Observed and calculated spectra covering the region from 740 cm(exp -1) and to 910 cm(exp -1) are presented. A compilation of transition frequencies, line intensities, and lower state energies are included for general use in the astronomical community.

Weber, Mark↗

DOE OSTI2025

Conformationally Adaptable Extractant Flexes Strong Lanthanide Reverse-Size Selectivity

Chemical selectivity is traditionally understood in the context of rigid molecular scaffolds with precisely defined local coordination and chemical environments that ultimately facilitate a given transformation of interest. By contrast, nature leverages dynamic structures and strong coupling to enable specific interactions with target species in otherwise complex media. Taking inspiration from nature, we demonstrate unconventional selectivity in the solvent extraction of light over heavy lanthanides using a conformationally flexible ligand called octadecyl acyclopa (ODA). This novel ligand forms pseudocyclic molecular complexes with lanthanide ions at organic/aqueous interfaces, revealed by vibrational sum frequency generation spectroscopy. These complexes are extracted into the organic phase, where femtosecond structural dynamics are probed by two-dimensional infrared spectroscopy and ab initio molecular dynamics simulations to mechanistically frame the macroscopic selectivity trends. We find larger-than-expected structural fluctuations and bond lengths for heavy Ln–ODA complexes that arise from an inability of ODA to contort around the smaller ions to satisfy all would-be bonding interactions, despite forming some individually strong bonds. This finding contrasts with the binding of ODA with lighter lanthanides where, despite individually weaker bonds, collective interactions manifest that minimize structural fluctuations and give rise to enhanced thermodynamic stability. Furthermore, these results point to a new paradigm where conformational dynamics and cumulative bonding interactions can be used to facilitate unconventional chemical transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗