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At least 811 records · Page 45

Basic research and data analysis for the National Geodetic Satellite program and for the Earth Surveys program

Current research is reported on precise and accurate descriptions of the earth's surface and gravitational field and on time variations of geophysical parameters. A new computer program was written in connection with the adjustment of the BC-4 worldwide geometric satellite triangulation net. The possibility that an increment to accuracy could be transferred from a super-control net to the basic geodetic (first-order triangulation) was investigated. Coordinates of the NA9 solution were computed and were transformed to the NAD datum, based on GEOS 1 observations. Normal equations from observational data of several different systems and constraint equations were added and a single solution was obtained for the combined systems. Transformation parameters with constraints were determined, and the impact of computers on surveying and mapping is discussed.

Source record↗

Iterative explicit guidance for low thrust spacecraft.

A retargeting procedure is developed for use as a nonlinear low thrust guidance scheme. The selection of a control program composed of a sequence of inertially fixed thrust-acceleration vectors permits all trajectory computations to be made with closed form expressions, and allows the controls to be represented by constant parameters, thrust-acceleration vectors and thrusting times. By requiring each trajectory to be time optimal, the guidance problem is transformed into a parameter optimization problem which is solved by the conjugate gradient method. The scheme is applied to a low thrust capture mission, and the results of computer simulations are presented.

Jacobson, R. A.↗

Meaningful experiences in science education: Engaging the space researcher in a cultural transformation to greater science literacy

The visceral appeal of space science and exploration is a very powerful emotional connection to a very large and diverse collection of people, most of whom have little or no perspective about what it means to do science and engineering. Therein lies the potential of space for a substantially enhanced positive impact on culture through education. This essay suggests that through engaging more of the space research and development community in enabling unique and 'meaningful educational experiences' for educators and students at the pre-collegiate levels, space science and exploration can amplify its positive feedback on society and act as an important medium for cultural transformation to greater science literacy. I discuss the impact of space achievements on people and define what is meant by a 'meaningful educational experience,' all of which points to the need for educators and students to be closer to the practice of real science. I offer descriptions of two nascent science education programs associated with NASA which have the needed characteristics for providing meaningful experiences that can cultivate greater science literacy. Expansion of these efforts and others like it will be needed to have the desired impact on culture, but I suggest that the potential for the needed resources is there in the scientific research communities. A society in which more people appreciate and understand science and science methods would be especially conducive to human progress in space and on Earth.

Morrow, Cherilynn A.↗

SatCORPS Global Cloud Composite (GCC): the Design and Delivery of A High Quality, High Resolution, Global Cloud Product Available in Near-Real Time

The NASA Satellite ClOud and Radiation Property retrieval System (SatCORPS) supports the development of an analysis ready and cloud-optimized data transformation pipeline and geospatial service enablement of a global cloud composite (GCC) product derived from global geostationary satellite imagery. This geospatial service will be available at high temporal and spatial resolution via the SatCORPS web mapping application for visualization and analysis as well as direct ingestion to common geospatial software and custom programming. The resulting global cloud composite products from the processing pipeline can then be geospatially-service enabled as ArcGIS Image Services and Open Geospatial Consortium (OGC) Web Mapping/Coverage Services for visualization and analysis via a web mapping application and common geospatial software. Near real time global observations are created through the composition of five geostationary satellites that provides modelling and forecasting communities with the capability to provide high quality and timely information to start the projection process. The Global Cloud Composite product combines information from geostationary satellites, GOES-16, GOES-17, Himawari-8, Meteosat-11 and Meteosat-9 to create a single global composite netcdf file and images using the different products within the netcdf file. The SatCORPS team, though our Global Cloud Composite (GCC) product and web-based visualization tools including Geographical Information System (GIS) services provide near real time global cloud product information to both automated processes and traditional web users that is timely and high quality derived from geostationary satellites. The Global Cloud Composite product takes advantage of the scalable processing resources provided by the AWS batch service to provide new composites every thirty minutes. Because information from each of the low earth orbiting satellites is available on schedules tuned to the specific satellite, the processing algorithm temporally composites the final dataset as each satellite’s information becomes available. The SatCORPS team has leveraged our experience using Amazon Web Services (AWS) to build a low latency high availability tool that allows end users both human and automated to acquire high quality and high-resolution Geostationary Earth Orbiting (GEO) information at zero cost to the end user. This presentation will describe how we architected and implemented the service as well as lessons learned based on our experiences both developing and operating the system. The lessons learned include how we integrated multiple services including Amazon Batch, Amazon S3 and Amazon Lambda service to create a low cost but high-performance processing system that is capable of identifying and processing the most appropriate satellite overpass information into global cloud composites. We will also describe our web-based tools including our Geographic Information System that can be used for visualization and analysis. The products from the processing can be geospatially-service enabled as ArcGIS Image Services and Open Geospatial Consortium (OGC) Web Mapping/Coverage Services for visualization and analysis via a web mapping application and common geospatial software. The SatCORPS Global Composite Cloud product provides sophisticated global composited cloud research products with very low latency that we see that as filling a rapidly growing need in the research and modelling community with no up-front nor ongoing costs associated with downloading or using the information.

AWS AMCE SMCE GCC SATCORPS GLOBAL CLOUD COMPOSITE ↗

Microchannel-based Membrane-less Extraction of Li from Unconventional Lithium Sources & the Separation of REE

This final report provides an overview of the Project's entire duration, covering July 1, 2021 to December 31, 2023. It primarily focuses on the achievements, technological developments, and unique challenges the team faced while working on separating and extracting Lithium from produced waters. The project's primary aim was to create an integrated, high-throughput, membrane-less, and modular microfluidic platform that could extract Lithium from unconventional sources. We have successfully met all goals and milestones envisioned in the SOPO document. The most critical primary milestones, including the Go-No-Go milestone (refer to the Gantt chart in the Appendices), were successfully accomplished. We demonstrated phase separation (>90%) and extraction (>85%) performance in the MPSE using synthetic, and representative produced water composition feed at 50 ml/min total flow through MPSE 36. We have also performed a parametric study of the MPSE operations, beyond the scope of SOPO, exploring operating conditions of current and broader interest. The extended investigation of operational parameters is concurrent with our efforts to seek further development of the MPSE technology beyond the scope of the Project. Along these lines of development, we have made efforts to be responsive to DOE calls for technological developments of other types of resources (beyond PW) for the recovery of Critical Materials and higher TRL development (beyond TRL 4). During the work on this Project, we developed and implemented three innovative technical approaches that emerged from our efforts to successfully meet the Project milestones. The innovative & original technical approaches developed and implemented in this Project are now the contributions to process engineering that could be clearly credited to the Project. First, Convergent Design Approach is a comprehensive feedforward & feedback loop of four design phases: i) design for functionality, ii) design for manufacturing, iii) design for sustainability, and iv) design for market. Next was Process Intensification. A major aim of this Project was to create an innovative phase separation & extraction microscale-based technology for Li separation – thus the words microchannel-based in the Project title. A microscale-based technology is intrinsically in the center of the Process Intensification domain as defined by its unique principles. Therefore, Process Intensification was implicitly envisioned in the Project’s SOPO. Lastly, Time Scale Analysis is a novel tool for discovering the needs and directions of Process Intensification implementations in any process technology. This Project is fully credited for developing and implementing the three novel technical approaches mentioned above. These are general contributions to process engineering that emerged from this Project. Beyond the original SOPO scope, the OSU-U.Pitt research group utilized a Convergent Design methodology, integrating first-principles mathematical modeling with experimental validation on the Minimum Development Vehicle. By creating these Digital Twins, the team rapidly assessed manufacturing iterations to support TEA analysis. This framework further enabled the development of advanced Surface Modification Techniques, where hydrophobic and oleophobic coating strategies were optimized via Digital Twin tools and validated through rigorous 100-hour longevity testing. TEA Analysis: The closing efforts of this Project were focused on the TEA analysis. TEA analysis had two primary functions: i) enabling critical assessments of design variations withing 10 the Concurrent Design Approach, thus enabling evolution of the MPSE design to reach faster- better-cheaper alternatives; and ii) to create a bridge between the accomplishments of this Project and future projects of higher TRL, beyond TRL 6 level. It is important to note that the TEA model created in the Project stirred the technological solutions for the recovery of critical materials toward a vision of a very profitable modular plant that has unique zero-waste water discharge signature. More importantly, thanks to our experimental performance data and conservative assumptions, the TEA model predicts minimal technological and investment risks. Low cost of a modular unit of a nominal capacity of [1000 tons of Li 2 CO 3 /year] positions the MPSE based technology within the reach of community investors, thus offering a paradigm shift in the development of critical technologies. The project successfully navigated two primary challenges: solvent selection and manufacturing adaptation. Restricted by the SOPO to existing literature for lithium recovery, the team identified a critical need for a "material excellence program" to develop next-generation solvents, eventually concluding with a preliminary investigation into promising Ionic Liquids (ILs). Simultaneously, COVID-19 supply chain disruptions forced a pivot from traditional manufacturing to advanced additive methods at ATAMI-OSU. By transitioning from stainless steel to 3D-printed polymer substrates, the team achieved a transformative three-order-of- magnitude reduction in manufacturing costs and compressed prototyping timelines from several months to just two days. The MPSE technology offers significant energy, environmental, and economic advantages by overcoming the traditional bottlenecks of phase-separation hardware and contactor size. Unlike conventional mixer-settlers or membrane-based systems, MPSE operates without moving parts or fouling-prone membranes, achieving robust performance even with challenging, viscous, or particulate-heavy feeds. Key performance metrics include an energy intensity reduction of 5–50x (3–40 kJ/m 3 ) compared to incumbent technologies and a dramatic reduction of processing time to under 60 seconds, which drastically reduces the physical plant footprint. These technical efficiencies translate into superior economic outcomes; for a 100 t/year Li 2 CO 3 facility, implementing MPSE is projected to nearly halve contactor CAPEX (from $\$$6.08M to $\$$3.01M) and significantly increase the project's Net Present Value (NPV), derisking new investment and enabling distributed critical-mineral processing configurations. The commercialization of MPSE technology is being spearheaded by Vigsur Dynamics Inc., which has adopted a structured, parallel approach to technical and business development since its formation in January 2026. Following extensive customer discovery and engagement with the Oregon State University accelerator, Vigsur Dynamics is working to establish a business model that transitions from pilot demonstrations to modular hardware sales, ultimately aiming for a "build-own-operate" service strategy. Current technical milestones—including 100 hours of continuous operation, superior energy efficiency, and successful 6-unit modular scale-up— provide a foundation for this transition. Backed by ongoing IP licensing and a growing network of industrial and venture advisors, the company is actively de-risking the platform to replace conventional mixer-settler systems in the critical minerals market.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generation of uniform chromaticity scale imagery from LANDSAT data

An algorithm is presented for generating uniform chromaticity scale (UCS) imagery from multispectral data. A computer program was written to implement the algorithm, and UCS film products were generated. The colors in the film and their temporal change are consistent with those expected for the particular scaling of Krauth components into the (lab) color space. The film product was not subjected to the practical test of competing with previous transformations. Preliminary examination indicates that the product offers the following possibilities: (1) a single film product that will supplant two film products in current use; (2) improved visibility of data differences in regions in data space that are critical to crop identification; and (3) an analytic route to the determination of data-space transformations that will be optimal for particular discrimination problems.

Juday, R. D.↗

Prepreg cure monitoring using diffuse reflectance-FTIR

An in situ diffuse reflectance-Fourier transform infrared technique was developed to determine infrared spectra of graphite fiber prepregs as they were being cured. A bismaleimide, an epoxy, and addition polyimide matrix resin prepregs were studied. An experimental polyimide adhesive was also examined. Samples were positioned on a small heater at the focal point of diffuse reflectance optics and programmed at 15 F/min while FTIR spectra were being scanned, averaged, and stored. An analysis of the resulting spectra provided basic insights into changes in matrix resin molecular structure which accompanied reactions such as imidization and crosslinking. An endo-exothermal isomerization involving reactive end-caps was confirmed for the addition polyimide prepregs. The results of this study contribute to a fundamental understanding of the processing of composites and adhesives. Such understanding will promote the development of more efficient cure cycles.

Young, P. R.↗

New correction procedures for the fast field program which extend its range

A fast field program (FFP) algorithm was developed based on the method of Lee et al., for the prediction of sound pressure level from low frequency, high intensity sources. In order to permit accurate predictions at distances greater than 2 km, new correction procedures have had to be included in the algorithm. Certain functions, whose Hankel transforms can be determined analytically, are subtracted from the depth dependent Green's function. The distance response is then obtained as the sum of these transforms and the Fast Fourier Transformation (FFT) of the residual k dependent function. One procedure, which permits the elimination of most complex exponentials, has allowed significant changes in the structure of the FFP algorithm, which has resulted in a substantial reduction in computation time.

West, M.↗

The Auto-Gopher Deep Drill

Subsurface penetration by coring, drilling or abrading is of great importance for a large number of space and earth applications. An Ultrasonic/Sonic Drill/Corer (USDC) has been in development at JPL's Nondestructive Evaluation and Advanced Actuators (NDEAA) lab as an adaptable tool for many of these applications. The USDC uses a novel drive mechanism to transform the high frequency ultrasonic or sonic vibrations of the tip of a horn into a lower frequency sonic hammering of a drill bit through an intermediate free-flying mass. The USDC device idea has been implemented at various scales from handheld drills to large diameter coring devices. A series of computer programs that model the function and performance of the USDC device were developed and were later integrated into an automated modeling package. The USDC has also evolved from a purely hammering drill to a rotary hammer drill as the design requirements increased form small diameter shallow drilling to large diameter deep coring. A synthesis of the Auto-Gopher development is presented in this paper.

Badescu, Mircea↗

NASTRAN modifications for recovering strains and curvatures

NASTRAN, NASA's general-purpose finite-element structural analysis program, has been modified to allow recovery of surface strains, reference plane strains, and local curvatures at nodes of general plane elements. NASTRAN routines that operate on element stress/strain/temperature relationships and strain/temperature relationships have been modified to incorporate generation and return of strains and curvatures in lieu of stresses. Strains and curvatures are then transformed to material axes and interpolated to generate corresponding strains and curvatures at nodes of element. This interpolation is accomplished using special surface-mapping function.

Chamis, C. C.↗

Combined effect of noise and vibration on passenger acceptance

An extensive research program conducted at NASA Langley Research Center to develop a comprehensive model of passenger comfort response to combined noise and vibration environments has been completed. This model was developed for use in the prediction and/or assessment of vehicle ride quality and as a ride quality design tool. The model has the unique capability to transform individual elements of vehicle interior noise and vibration into subjective units and combining the subjective units to produce a total subjective discomfort index as well as the other useful subjective indices. This paper summarizes the basic approach used in the development of the NASA ride comfort model, presents some of the more fundamental results obtained, describes several application of the model to operational vehicles, and discusses a portable, self-contained ride quality meter system that is a direct hardware/software implementation of the NASA comfort algorithm.

Leatherwood, J. D.↗

MAX '91: An advanced payload for the exploration of high energy processes on the active sun

The results of a NASA science working group established to study a follow-on to the Solar Maximum Mission are given. A complement of instruments is suggested, with the primary objective of studying the physics of energetic processes in cosmic plasmas by observing high-energy phenomena in solar flares. High-quality flare observations will be possible with these instruments during the next peak in solar activity expected to last from 1990 through at least 1995. The primary objective of MAX '91 is to study energetic processes in cosmic plasmas by observing high-energy phenomena in solar flares. These processes, which are of general astrophysical importance, include energy release, particle acceleration, and energy transport. Results from comprehensive observing programs conducted during the last solar cycle have demonstrated the great scientific potential of high-energy emissions for addressing these central physical processes. Consequently, a payload optimized for observations of high-energy solar flare phenomena is suggested for MAX '91. It consists of the following four specific instruments: (1) a Fourier-transform X-ray and gamma-ray imager covering the energy range from a few keV to 1 MeV with arcsecond spatial resolution; (2) a cooled germanium X-ray and gamma-ray spectrometer with keV spectral resolution covering the energy range from 10 keV to 50 MeV; (3) Bragg spectrometers with high spectral resolution at wavelengths between 1 and 9 angstrons; and (4) a soft X-ray, EUV, or UV imaging instrument with arcsecond spatial resolution.

Source record↗

Developing Tests of Visual Dependency

Astronauts develop neural adaptive responses to microgravity during space flight. Consequently these adaptive responses cause maladaptive disturbances in balance and gait function when astronauts return to Earth and are re-exposed to gravity. Current research in the Neuroscience Laboratories at NASA-JSC is focused on understanding how exposure to space flight produces post-flight disturbances in balance and gait control and developing training programs designed to facilitate the rapid recovery of functional mobility after space flight. In concert with these disturbances, astronauts also often report an increase in their visual dependency during space flight. To better understand this phenomenon, studies were conducted with specially designed training programs focusing on visual dependency with the aim to understand and enhance subjects ability to rapidly adapt to novel sensory situations. The Rod and Frame test (RFT) was used first to assess an individual s visual dependency, using a variety of testing techniques. Once assessed, subjects were asked to perform two novel tasks under transformation (both the Pegboard and Cube Construction tasks). Results indicate that head position cues and initial visual test conditions had no effect on an individual s visual dependency scores. Subjects were also able to adapt to the manual tasks after several trials. Individual visual dependency correlated with ability to adapt manual to a novel visual distortion only for the cube task. Subjects with higher visual dependency showed decreased ability to adapt to this task. Ultimately, it was revealed that the RFT may serve as an effective prediction tool to produce individualized adaptability training prescriptions that target the specific sensory profile of each crewmember.

Kindrat, Alexandra N.↗

Kennedy Space Center: Apollo to Multi-User Spaceport

NASA Kennedy Space Center (KSC) was established as the gateway to exploring beyond earth. Since the establishment of KSC in December 1963, the Center has been critical in the execution of the United States of Americas bold mission to send astronauts beyond the grasp of the terra firma. On May 25, 1961, a few weeks after a Soviet cosmonaut became the first person to fly in space, President John F. Kennedy laid out the ambitious goal of landing a man on the moon and returning him safely to the Earth by the end of the decade. The resultant Apollo program was massive endeavor, driven by the Cold War Space Race, and supported with a robust budget. The Apollo program consisted of 18 launches from newly developed infrastructure, including 12 manned missions and six lunar landings, ending with Apollo 17 that launched on December 7, 1972. Continuing to use this infrastructure, the Skylab program launched four missions. During the Skylab program, KSC infrastructure was redesigned to meet the needs of the Space Shuttle program, which launched its first vehicle (STS-1) on April 12, 1981. The Space Shuttle required significant modifications to the Apollo launch pads and assembly facilities, as well as new infrastructure, such as Orbiter and Payload Processing Facilities, as well as the Shuttle Landing Facility. The Space Shuttle was a workhorse that supported many satellite deployments, but was key for the construction and maintenance of the International Space Station, which required additional facilities at KSC to support processing of the flight hardware. After reaching the new Millennium, United States policymakers searched for new ways to reduce the cost of space exploration. The Constellation Program was initiated in 2005 with a goal of providing a crewed lunar landing with a much smaller budget. The very successful Space Shuttle made its last launch on July 8, 2011, after 135 missions. In the subsequent years, KSC continues to evolve, and this paper will address past and future efforts of the transformation of the KSC Apollo and Space Shuttle heritage infrastructure into a more versatile, multi-user spaceport. The paper will also discuss the US Congressional and NASA initiatives for developing and supporting multiple commercial partners, while simultaneously supporting NASAs human exploration initiative, consisting of Space Launch System (SLS), Orion spacecraft and associated ground launch systems. In addition, the paper explains the approach with examples for NASA KSC to leverage new technologies and innovative capabilities developed to reduce the cost to individual users.

launchpad↗

Adjoint methods for aerodynamic wing design

A model inverse design problem is used to investigate the effect of flow discontinuities on the optimization process. The optimization involves finding the cross-sectional area distribution of a duct that produces velocities that closely match a targeted velocity distribution. Quasi-one-dimensional flow theory is used, and the target is chosen to have a shock wave in its distribution. The objective function which quantifies the difference between the targeted and calculated velocity distributions may become non-smooth due to the interaction between the shock and the discretization of the flowfield. This paper offers two techniques to resolve the resulting problems for the optimization algorithms. The first, shock-fitting, involves careful integration of the objective function through the shock wave. The second, coordinate straining with shock penalty, uses a coordinate transformation to align the calculated shock with the target and then adds a penalty proportional to the square of the distance between the shocks. The techniques are tested using several popular sensitivity and optimization methods, including finite-differences, and direct and adjoint discrete sensitivity methods. Two optimization strategies, Gauss-Newton and sequential quadratic programming (SQP), are used to drive the objective function to a minimum.

Grossman, Bernard↗

Issues and Methods Concerning the Evaluation of Hypersingular and Near-Hypersingular Integrals in BEM Formulations

It is known that higher order modeling of the sources and the geometry in Boundary Element Modeling (BEM) formulations is essential to highly efficient computational electromagnetics. However, in order to achieve the benefits of hIgher order basis and geometry modeling, the singular and near-singular terms arising in BEM formulations must be integrated accurately. In particular, the accurate integration of near-singular terms, which occur when observation points are near but not on source regions of the scattering object, has been considered one of the remaining limitations on the computational efficiency of integral equation methods. The method of singularity subtraction has been used extensively for the evaluation of singular and near-singular terms. Piecewise integration of the source terms in this manner, while manageable for bases of constant and linear orders, becomes unwieldy and prone to error for bases of higher order. Furthermore, we find that the singularity subtraction method is not conducive to object-oriented programming practices, particularly in the context of multiple operators. To extend the capabilities, accuracy, and maintainability of general-purpose codes, the subtraction method is being replaced in favor of the purely numerical quadrature schemes. These schemes employ singularity cancellation methods in which a change of variables is chosen such that the Jacobian of the transformation cancels the singularity. An example of the sin,oularity cancellation approach is the Duffy method, which has two major drawbacks: 1) In the resulting integrand, it produces an angular variation about the singular point that becomes nearly-singular for observation points close to an edge of the parent element, and 2) it appears not to work well when applied to nearly-singular integrals. Recently, the authors have introduced the transformation u(x(prime))= sinh (exp -1) x(prime)/Square root of ((y prime (exp 2))+ z(exp 2) for integrating functions of the form I = Integral of (lambda(r(prime))((e(exp -jkR))/(4 pi R) d D where A (r (prime)) is a vector or scalar basis function and R = Square root of( (x(prime)(exp2) + (y(prime)(exp2) + z(exp 2)) is the distance between source and observation points. This scheme has all of the advantages of the Duffy method while avoiding the disadvantages listed above. In this presentation we will survey similar approaches for handling singular and near-singular terms for kernels with 1/R(exp 2) type behavior, addressing potential pitfalls and offering techniques to efficiently handle special cases.

Fink, P. W.↗

Simple and Efficient Numerical Evaluation of Near-Hypersingular Integrals

Recently, significant progress has been made in the handling of singular and nearly-singular potential integrals that commonly arise in the Boundary Element Method (BEM). To facilitate object-oriented programming and handling of higher order basis functions, cancellation techniques are favored over techniques involving singularity subtraction. However, gradients of the Newton-type potentials, which produce hypersingular kernels, are also frequently required in BEM formulations. As is the case with the potentials, treatment of the near-hypersingular integrals has proven more challenging than treating the limiting case in which the observation point approaches the surface. Historically, numerical evaluation of these near-hypersingularities has often involved a two-step procedure: a singularity subtraction to reduce the order of the singularity, followed by a boundary contour integral evaluation of the extracted part. Since this evaluation necessarily links basis function, Green s function, and the integration domain (element shape), the approach ill fits object-oriented programming concepts. Thus, there is a need for cancellation-type techniques for efficient numerical evaluation of the gradient of the potential. Progress in the development of efficient cancellation-type procedures for the gradient potentials was recently presented. To the extent possible, a change of variables is chosen such that the Jacobian of the transformation cancels the singularity. However, since the gradient kernel involves singularities of different orders, we also require that the transformation leaves remaining terms that are analytic. The terms "normal" and "tangential" are used herein with reference to the source element. Also, since computational formulations often involve the numerical evaluation of both potentials and their gradients, it is highly desirable that a single integration procedure efficiently handles both.

Fink, Patrick W.↗

Fundamental Studies of the Vibrational, Electronic, and Photophysical Properties of Tetrapyrrolic Architectures

The ability to capture and utilize light in the near-ultraviolet (NUV), visible and near-infrared (NIR-I and NIR-II) spectral regions (i.e., 320–400, 400–700, 700–1000, 1000–1700 nm) is essential for any solar-energy conversion scheme. Nature employs chlorophylls and bacteriochlorophylls in light-harvesting architectures to absorb light in the blue and red/NIR regions. Accessory pigments (carotenoids, bilins) augment absorption of the (bacterio)chlorophylls in the green region. The harvested energy is funneled to a reaction center protein, where charge separation occurs. Subsequent migration of the electron and the hole stabilizes and stores the energy from light via redox chemistry. The long-term objective of the Bocian/Holten&Kirmaier/Lindsey research program under this DOE grant has been to develop tetrapyrrole-based molecular architectures that absorb sunlight, funnel energy and separate charge with high efficiency. Integral to the program has been iterative cycles of design, synthesis and characterization that provided deep insights into the relationships between chemical composition, electronic structure, and key static and dynamic properties (vibrational, redox, photophysical, energy/charge transfer) of tetrapyrrolic systems. Such architectures included monomers, dyads, larger arrays, and complexes with accessory components. The objective was to develop molecular designs and guiding principles to enhance current and future energy-conversion schemes. Molecular arrays targeted to address one or more fundamental questions concerning light harvesting and energy/charge transfer were constructed from analogues of the naturally occurring hemes, chlorophylls and bacteriochlorophylls. Diverse, tunable synthetic building blocks were prepared that spanned the three respective tetrapyrrole families, which are the porphyrins, chlorins and bacteriochlorins. Thus, the research focused on porphyrins as well as synthetic surrogates for chlorophylls (chlorins, 13 1 -oxophorbines and chlorin-imides) and bacteriochlorophylls (bacteriochlorins, bacterio-13 1 -oxophorbines and bacteriochlorin-imides), generically termed hydroporphyrins. Although the three tetrapyrrole classes (porphyrins, chlorins and bacteriochlorins) absorb light strongly in the violet-blue spectral region, the long-wavelength absorption band typically lies in the green-orange, red, and NIR regions, respectively, with increasing intensity. Understanding the spectra, electronic structure, and energy/charge-transfer properties of such tetrapyrrolic macrocycles is of central importance for the rational design of molecular architectures for solar-energy conversion. Our integrated program of molecular design and synthesis coupled with a variety of spectroscopic, electrochemical, and computational studies have probed from first principles how structural and electronic properties of tetrapyrrolic macrocycles dictate spectral properties as well as the rates of ground-state hole/electron transfer and excited-state energy flow in multicomponent architectures. Individual molecules and multicomponent architectures were designed to test ideas of fundamental importance, often requiring the development of new synthetic methodology. The members of the collaborative team had almost daily discussions by phone and/or e-mail concerning design of molecules, flow of compounds between the labs, planning of physical characterization studies, discussing results and analysis and integrating into design of next generation architectures, and the preparation of manuscripts. Furthermore, students and postdocs in the different labs routinely communicated with one another to facilitate the advancement of the research activities. In short, a highly integrated and collaborative research program was well established among the groups. The research effort involved molecular design and synthesis of synthetic molecular architectures by the Lindsey group integrated with physicochemical and photophysical characterization by the Bocian group and the Holten&Kirmaier group (Figure 2). The Bocian group carried out electrochemical, electron paramagnetic resonance (EPR), resonance Raman (RR), and Fourier-transform infrared (FT-IR) studies, as well as density functional theory (DFT) calculations and the time-dependent extension (TDDFT) to gain insight into excited-state properties. The Holten&Kirmaier group carried out static and time-resolved absorption and fluorescence spectroscopy studies and simulated absorption spectra using molecular orbital (MO) energies from DFT as input to the four-orbital model to complement the TDDFT calculations. The combined measurements provided understanding of the vibrational/electronic properties of the individual molecules and the changes that occur upon incorporation into multicomponent architectures. This information underpinned elucidating the mechanisms and timescales of ground-state hole/electron transfer and excited-state energy and charge transfer.

14 SOLAR ENERGY↗