Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “optimal start”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 847 records · Page 47
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

On-line identification and attitude control for SCOLE

This paper documents on-line linear least-square identification and attitude control of SCOLE, a laboratory apparatus representing an offset-feed antenna attached to the Space Shuttle. Identification is done autonomously by starting a slew maneuver in pitch or roll with reaction jets and observing the time history data of associated Euler angles when the jets are quiescent. Linear least-square analysis is used to select the parameters that best fit the output of an Autoregressive (AR) model to the data. The control effectiveness of the jets is determined in a subsequent test, again using linear least squares. The parameters so derived are used to design switching lines for time-optimal attitude control. This report describes the identification and control algorithms and the experimental apparatus and procedures used. Also, experimental data are presented that reflect the performance of the identification algorithms and the attitude control system.

Montgomery, R. C.↗
NASA NTRS1993

Predicting scheduling success

This paper provides an analytical formulation to predict scheduling success for a class of problems frequently referred to as activity scheduling. Space Network communications scheduling is an example of activity scheduling. The principal assumption is that the activity start times are randomly distributed over the available time in the time line. The formulation makes it possible to estimate how much of the demand can be scheduled as a function of the demand, number of resources, activity duration, and activity flexibility. The paper includes computed results for a variety of resource and demand conditions. The results demonstrate that even with highly flexible activities, it is difficult to schedule demand greater than 60 percent of resources without the use of optimization and conflict resolution capabilities in the scheduling system.

Messing, Fredric↗
NASA NTRS2015

Three Orbital Burns to Molniya Orbit Via Shuttle_Centaur G Upper Stage

An unclassified analytical trajectory design, performance, and mission study was done for the 1982 to 1986 joint National Aeronautics and Space Administration (NASA)-United States Air Force (USAF) Shuttle/Centaur G upper stage development program to send performance-demanding payloads to high orbits such as Molniya using an unconventional orbit transfer. This optimized three orbital burn transfer to Molniya orbit was compared to the then-baselined two burn transfer. The results of the three dimensional trajectory optimization performed include powered phase steering data and coast phase orbital element data. Time derivatives of the orbital elements as functions of thrust components were evaluated and used to explain the optimization's solution. Vehicle performance as a function of parking orbit inclination was given. Performance and orbital element data was provided for launch windows as functions of launch time. Ground track data was given for all burns and coasts including variation within the launch window. It was found that a Centaur with fully loaded propellant tanks could be flown from a 37 deg inclination low Earth parking orbit and achieve Molniya orbit with comparable performance to the baselined transfer which started from a 57 deg inclined orbit: 9,545 versus 9,552 lb of separated spacecraft weight, respectively. There was a significant reduction in the need for propellant launch time reserve for a 1 hr window: only 78 lb for the three burn transfer versus 320 lb for the two burn transfer. Conversely, this also meant that longer launch windows over more orbital revolutions could be done for the same amount of propellant reserve. There was no practical difference in ground tracking station or airborne assets needed to secure telemetric data, even though the geometric locations of the burns varied considerably. There was a significant adverse increase in total mission elapsed time for the three versus two burn transfer (12 vs. 1-1/4 hr), but could be accommodated by modest modifications to Centaur systems. Future applications were discussed. The three burn transfer was found to be a viable, arguably preferable, alternative to the two burn transfer.

Orbital trajectory design↗
NASA NTRS2018

Predictive Thermal Control (PTC) Technology to Enable Thermally Stable Telescopes

The Predictive Thermal Control (PTC) technology development project is a multiyear effort initiated in Fiscal Year (FY) 2017, to mature the Technology Readiness Level (TRL) of critical technologies required to enable ultra-thermally-stable telescopes for exoplanet science. During 2017/18 PTC has successfully progressed its three defined objectives: 1. Validate thermal optical performance models. 2. Derive thermal system stability specifications. 3. Demonstrate Predictive Thermal Control. by accomplishing or advancing three of its five quantifiable milestones: Milestone #1 (Complete): Created a high-fidelity STOP (Structural-Thermal-Optical-Performance) model of the1.5 meter ULE® AMTD (Advanced Mirror Technology Development)-2 mirror, including 3D CTE (Coefficient of Thermal Expansion) distribution and reflective coating, that predicts its optical performance response to steady-state and dynamic thermal gradients. Structural model was created using 3D X-Ray Computed Tomography; Milestone #2 (Complete): Derived specifications for thermal control system as a function of wavefront stability for a Vector Vortex Coronagraph; Milestone #3 (In-Process): Designed and started fabricating a predictive Thermal Control System for the AMTD-2 1.5 meter ULE® mirror that senses temperature changes and actively controls the mirror's thermal environment; Milestone #4 (In-Process): Performed preliminary STOP model validation tests of the 1.5-m ULE® mirror in a relevant thermal vacuum environment at the MSFC X-ray and Cryogenic Facility (XRCF) test facility; Milestone #5: Use validated model to perform trade studies to determine how thermo-optical performance can be optimized as a function of mirror design, material selection, mass, etc.

Stahl, H. Philip↗
DOE OSTI2022

Design of protein-binding proteins from the target structure alone

The design of proteins that bind to a specific site on the surface of a target protein using no information other than the three-dimensional structure of the target remains a challenge. Here we describe a general solution to this problem that starts with a broad exploration of the vast space of possible binding modes to a selected region of a protein surface, and then intensifies the search in the vicinity of the most promising binding modes. We demonstrate the broad applicability of this approach through the de novo design of binding proteins to 12 diverse protein targets with different shapes and surface properties. Biophysical characterization shows that the binders, which are all smaller than 65 amino acids, are hyperstable and, following experimental optimization, bind their targets with nanomolar to picomolar affinities. We succeeded in solving crystal structures of five of the binder–target complexes, and all five closely match the corresponding computational design models. Experimental data on nearly half a million computational designs and hundreds of thousands of point mutants provide detailed feedback on the strengths and limitations of the method and of our current understanding of protein–protein interactions, and should guide improvements of both. Our approach enables the targeted design of binders to sites of interest on a wide variety of proteins for therapeutic and diagnostic applications.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2012

Status Update on the James Webb Space Telescope Project

The James Webb Space Telescope (JWST) is a large (6.6 m), cold <50 K), infrared (IR)-optimized space observatory that will be launched in approx.2018. The observatory will have four instruments covering 0.6 to 28 micron, including a multi-object spectrograph, two integral field units, and grisms optimized for exoplanets. I will review JWST's key science themes, as well as exciting new ideas from the recent JWST Frontiers Workshop. I will summarize the technical progress and mission status. Recent highlights: All mirrors have been fabricated, polished, and gold-coated; the mirror is expected to be diffraction-limited down to a wavelength of 2 microns. The MIRI instrument just completed its cryogenic testing. STScI has released exposure time calculators and sensitivity charts to enable scientists to start thinking about how to use JWST for their science.

Rigby, Jane R.↗
NASA NTRS2016

Computational Study of Flow Interactions in Coaxial Rotors

Although the first idea of coaxial rotors appeared more than 150 years ago, most helicopters have used single main-rotor/tail-rotor combination. Since reactive moments of coaxial rotors are canceled by contra-rotation, no tail rotor is required to counter the torque generated by the main rotor. Unlike the single main rotor design that distributes power to both main and tail rotors, all of the power for coaxial rotors is used for vertical thrust. Thus, no power is wasted for anti-torque or directional control. The saved power helps coaxial rotors reach a higher hover ceiling than single rotor helicopters. Another advantage of coaxial rotors is that the overall rotor diameter can be reduced for a given vehicle gross weight because each rotor provides a maximum contribution to vertical thrust to overcome vehicle weight. However, increased mechanical complexity of the hub has been one of the challenges for manufacturing coaxial rotorcraft. Only the Kamov Design Bureau of Russia had been notably successful in production of coaxial helicopters until Sikorsky built X2, an experimental compound helicopter. Recent developments in unmanned aircraft systems and high-speed rotorcraft have renewed interest in the coaxial configuration. Multi-rotors are frequently used for small electric unmanned rotorcraft partly due to mechanical simplicity. The use of multiple motors provides redundancy as well as cost-efficiency. The multi-rotor concept has rarely been used until recently because of its inherent stability and control problems. However, advances in inexpensive electronic flight control systems have opened the floodgates for small drones using multirotors. Coaxial rotors have started to appear in some multi-rotor configurations. Small coaxial rotors have often been designed using a hundred year old approach that is "sketch, build, fly, and iterate." In that approach, there is no systematic way to explore trade-offs or determine logical next steps. It is neither possible to account for multiple real-world constraints up front in design nor possible to know what performance is possible with a given design. Since unmanned vehicles are sized and optimized for the particular mission, a modern low-fidelity conceptual design and sizing tool that has been used for the design of large helicopters can be used for design of small coaxial rotorcraft. However, unlike most helicopters with single main rotor, the interactions between the upper and lower rotors emerge as an important factor to consider in design because an increase in performance of a multi-rotor system is not proportional to the number of rotors. Interference losses and differences in thrusts between the upper and lower rotors were investigated by theoretical methods as well as a computational fluid dynamics (CFD) method using the Reynolds-Averaged Navier-Stokes (RANS) equations. In this work, hybrid turbulence models are used to investigate the physics of interactions between coaxial rotors and a fuselage that are not well understood. Present study covers not only small-scale drones but also large-scale coaxial rotors for heavy-lifting missions. Considering the recently proposed FAA drone rules that require the flight only in visual line-of-sight, a large multirotor might be used as an airborne carrier for launch and recovery of unmanned aircraft systems with a human operator onboard. For applications to civil operations, their aerodynamic performance and noise levels need to be assessed. Noise is one of the largest limiting factors to rotorcraft operations in urban area. Since the high-frequency noise of multi-rotors may increase the annoyance, noise may turn out to be a key issue that must be addressed for market acceptability. One of the objectives of the present work is to study the effects of inter-rotor spacing and collectives on the performance, efficiency, and acoustics of coaxial rotor systems.

Study↗
DOE OSTI2020

Overview of Upcoming Process Improvement Efforts at the Saltstone Facilities at the Savannah River Site - 20474

The Saltstone Facilities at the Savannah River Site (SRS) process and dispose of low activity salt solution waste generated by other liquid waste facilities. Today in the Liquid Waste System (LWS), approximately 125 million liters of salt waste remain to be processed. The Saltstone Production Facility (SPF) receives the decontaminated salt waste, which is mixed with dry feeds consisting of cement, fly ash and slag to produce the saltstone. The mixed slurry is pumped to the Saltstone Disposal Units (SDUs) for safe disposal in the Saltstone Disposal Facility (SDF). To support continuous Salt Waste Processing Facility (SWPF) operations at annual processing volumes many times higher than present, significant modifications are required to ensure that the SPF has the capacity to support the throughput of salt waste. These changes include several infrastructure upgrades that are being worked through the Enhanced Low Activity Waste Disposal (ELAWD) project. In addition to infrastructure upgrades, Savannah River Remediation (SRR), the Savannah River Site's Liquid Waste Contractor for the U.S. Department of Energy, has identified a flowsheet improvement opportunity of implementing a cement-free saltstone formulation to eliminate cement from the current three component formulation. This two-component formulation would simplify the procurement, transport, off-loading, and storage of the premix materials, and increase the storage capacity for the individual components. This flowsheet, when implemented, will reduce operational risk and improve throughput necessary to achieve disposal rates necessary for SWPF operations. Research has been completed to confirm the feasibility of this formulation, with the new cement-free flowsheet expected to be implemented in the next few years. Improvements have also been identified downstream of the SPF to increase SDU utilization. Specifically, a concentrated effort has taken place to raise the fill height in SDU 6 to the full disposal height, 13 meters, to maximize the usage of each SDU in support of the liquid waste disposal mission. This improvement has been made through additional thermal modeling and improved process understanding to create a SDU flammability model and control strategy more representative of facility operations. This work will allow for the completion of construction and operational readiness for SDU 7 while filling SDU 6 to ensure there is no lapse in available space once SWPF starts up. A summary of these improvements as they relate to increased throughput will be provided along with associated status. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Role of Mg:Al ratio and Pt promotion on mitigating the deactivation of Ni-based methane steam reforming catalysts

Ni-based catalysts for CH 4 steam reforming require fine-tuning to withstand deactivation under dynamic operation conditions relevant to emerging H 2 -driven technologies. This study investigates the impact of the Mg:Al ratio and Pt presence in catalyst composition on the activity and stability of industrially relevant Ni-based mono- and bimetallic catalysts during simulated daily start-up and shut-down cycles in various gas atmospheres. The evolution of the catalyst structure during extensive testing procedures was investigated in detail by complementary electron microscopy, in situ/operando XAS and XRD. The results obtained revealed that catalyst deactivation is promoted at high Mg:Al ratios and especially affects the monometallic catalysts. By converting CH 4 at lower temperatures, Pt regulates the extent of Ni oxidation and its incorporation into MgO lattice. Further prevention of catalyst deactivation was achieved by optimizing the reactor shut-down procedure to minimize the simultaneous exposure to high temperatures and H 2 O vapors. By flushing the reactor with N 2 only around the reaction extinction temperature, a fraction of Ni species is maintained in metallic state, which is beneficial for the long-term activity and reaction operation economy.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Impact of Selected High-Performance Fuel Blends on Three-Way Catalyst Light Off under Synthetic Spark-Ignition Engine-Exhaust Conditions

The U.S. Department of Energy funded Co-Optimization of Fuels and Engines initiative aims to simultaneously develop advanced engines along with high-performance fuels to reduce petroleum consumption. The engine exhaust of spark-ignited light-duty vehicles contains pollutants such as nitrogen oxides, carbon monoxide (CO), and non-methane organic gases. When operated above their “light-off” temperature, three-way catalysts (TWCs) efficiently control the emissions of these pollutants from the vehicle exhaust. However, below the catalyst light-off temperature, during cold start, the TWCs are not effective. Thus, the stringent environmental regulations necessitate cold-start compliance of advanced engines operating on novel fuels for commercialization. Exhaust composition strongly impacts the effectiveness of TWCs. Hence, ensuring that the high-performance fuels under consideration do not have detrimental effects on current emissions control technology is necessary. To mitigate cold-start emissions, a low light-off temperature of the fuel on the TWC is desirable. As real-world fuels are multicomponent blends, we conducted investigations into the light-off behavior of representative fuel mixtures on a three-mode redox-aged commercial TWC under synthetic engine-exhaust conditions. The high-performance fuels in this study included 10–30% volumetric levels of ethanol, isobutanol, diisobutylene, and an aromatic mixture. Each of these high-performance fuel components was mixed into a gasoline surrogate blendstock for oxygenate blending (BOB). Our results showed that aromatics and alkenes in the surrogate BOB inhibit low-temperature reactivity of alkanes, alcohols, and CO on the TWC and dominate the blend light-off behavior. All the high-performance fuel blends had a very similar light-off behavior to the surrogate gasoline BOB, indicating that blending up to 30% (by vol.) of high-performance blendstocks in a gasoline base fuel can potentially reduce greenhouse gas emissions through improved engine efficiency and petroleum displacement without jeopardizing the ability to meet emissions regulations. While some high-performance blendstocks demonstrated lower light-off temperatures than a surrogate gasoline blend, taking advantage of the higher catalytic reactivity of these blendstocks to reduce cold-start emissions would require reducing the aromatic content in petroleum-based market fuels.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2020

Relativistic configuration-interaction and many-body-perturbation-theory calculations of U i hyperfine constants

Neutral uranium (U i) is a very difficult atom for theoretical calculations due to a large number (six) of valence electrons, strong valence-valence and valence-core correlations, high density of states, and relativistic effects. Configuration-interaction many-body perturbation theory (CI-MBPT) can efficiently treat valence-core correlations and relativistic effects, but because the formalism was developed for a Dirac-Hartree-Fock (DHF) starting potential that does not contain valence electrons, quite large CI space is needed to compensate for the + 6 charge of such a potential. Much more efficient is the relativistic configuration-interaction (RCI) approach, which uses a relatively accurate starting DHF potential that includes some valence electrons to make the valence-electron Hamiltonian diagonally dominated for some states. Here we report calculations of U i hyperfine constants of several low-energy states using the RCI method with the starting potential that includes four f valence electrons. With this starting potential, it is possible to use the single-configuration approximation or small basis sets to obtain quite accurate results for hyperfine-structure constants. In fact, by scaling the nuclear magnetic moment, the agreement for five levels was within 5% and a new magnetic moment can be recommended, 0.43(2). When two states are mixed, it is difficult to predict the exact mixing fractions, so in this case we proposed a method in which the mixing fraction is found by optimization of one parameter in the MBPT correction to obtain correct g factors. The resulting hyperfine constants are significantly improved. Finally, the CI-MBPT approach was also tested, with some success for low-energy states, with the limited basis set. The methods investigated here can be further developed to include more extensive data sets to improve accuracy and can be applied to other atoms and for calculations of other properties, for example, relevant to fundamental symmetry tests.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1998

Parallel Directionally Split Solver Based on Reformulation of Pipelined Thomas Algorithm

In this research an efficient parallel algorithm for 3-D directionally split problems is developed. The proposed algorithm is based on a reformulated version of the pipelined Thomas algorithm that starts the backward step computations immediately after the completion of the forward step computations for the first portion of lines This algorithm has data available for other computational tasks while processors are idle from the Thomas algorithm. The proposed 3-D directionally split solver is based on the static scheduling of processors where local and non-local, data-dependent and data-independent computations are scheduled while processors are idle. A theoretical model of parallelization efficiency is used to define optimal parameters of the algorithm, to show an asymptotic parallelization penalty and to obtain an optimal cover of a global domain with subdomains. It is shown by computational experiments and by the theoretical model that the proposed algorithm reduces the parallelization penalty about two times over the basic algorithm for the range of the number of processors (subdomains) considered and the number of grid nodes per subdomain.

Povitsky, A.↗
NASA NTRS2001

High Frequency, Long Time Series Measurements from the Bermuda Testbed Mooring in Support of SIMBIOS

It has been recognized that optical moorings are important platforms for the validation of Sea-Viewing Wide Field-of-view Sensor (SeaWiFS). It was recommended that optical moorings be maintained in order to: (1) provide long-term time series comparisons between in situ and SeaWIFS measurements of normalized water-leaving radiance; (2) develop and test algorithms for pigment biomass and phytoplankton primary productivity; and (3) provide long-term, virtually continuous in situ observations which can be used to determine and optimize the accuracy of derived satellite products. These applications require the use of in situ radiometers for long periods of time to evaluate and correct for inherent satellite undersampling (aliasing and biasing) and degradation of satellite color sensors (e.g., drifts as experienced by the Coastal Zone Color Scanner). The Bermuda Testbed Mooring (BTM) program was initiated in 1994 at a site located about 80km southeast of Bermuda in waters of about 4530 m depth. In August 1997, with NASA's support, we started to provide the Sensor Intercomparison and Merger for Biological and Interdisciplinary Oceanic Studies (SIMBIOS) program with large volumes of high frequency, long-term time-series bio-optical data from the BTM for SeaWiFS satellite ocean color groundtruthing and algorithm development. This NASA supported portion of the BTM activity spanned three years and covered five BTM deployments. During these three years, the quality of radiometric data has improved dramatically. Excellent agreement between BTM moored data and both SeaWiFS and nearby ship profile radiometric data demonstrate that technical advances in the moored optical observations have reduced the major difficulties that moored platforms face: biofouling and less frequent calibration.

Dickey, Tommy↗
DOE OSTI2020

On the Solution of ℓ 0 -Constrained Sparse Inverse Covariance Estimation Problems

The sparse inverse covariance matrix is used to model conditional dependencies between variables in a graphical model to fit a multivariate Gaussian distribution. Estimating the matrix from data are well known to be computationally expensive for large-scale problems. Sparsity is employed to handle noise in the data and to promote interpretability of a learning model. Although the use of a convex ℓ 1 regularizer to encourage sparsity is common practice, the combinatorial ℓ 0 penalty often has more favorable statistical properties. In this paper, we directly constrain sparsity by specifying a maximally allowable number of nonzeros, in other words, by imposing an ℓ 0 constraint. Here, we introduce an efficient approximate Newton algorithm using warm starts for solving the nonconvex ℓ 0 -constrained inverse covariance learning problem. Numerical experiments on standard data sets show that the performance of the proposed algorithm is competitive with state-of-the-art methods.

$\ell_0$-Constrained↗
DOE OSTI2022

Temperature-Dependent Thermal and Mechanical Properties of a Wire Arc Additively Manufactured Low Transformation Temperature Steel

Recent research has studied the use of low transformation temperature (LTT) martensite steel as feedstock for wire arc additive manufacturing (WAAM) and low tensile residual stresses or compressive residual stresses were detected in the printed walls. These residual stress states help to improve printed product properties such as fatigue strength and corrosion resistance. However, the thermal and mechanical properties of WAAM printed LTT martensite steel walls are largely unknown. In this work, a printed LTT martensite steel was characterized for its thermal, metallurgical, and mechanical behavior at room and elevated temperatures. The temperature-dependent specific heat capacity, thermal expansion, atomic lattice spacing, and tensile properties were measured during both heating and cooling and related to observed microstructural features and computational thermodynamics predictions. These results revealed a large hysteresis in the martensitic transformation, with a martensite start temperature of 240 °C and austenite start temperature of 680 °C. Additional thermal cycles and specimen orientation did not affect the printed specimen austenite and martensite transformations. However, it was observed that the printed metal may exhibit tempering embrittlement at about 350 °C but further studies are needed to confirm that. Further, these results suggest that a temperature control of 250 °C to 350 °C during WAAM is needed to maximize the stress reduction potential of the LTT250 martensite steel. Opportunities for future implementation of LTT martensite steels and optimization of additive manufacturing process conditions are identified.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Process and feedstock driven microstructure for laser powder bed fusion of 316L stainless steel

Here in the pursuit of improving additively manufactured (AM) component quality and reliability, fine-tuning critical process parameters such as laser power and scan speed is a great first step toward limiting defect formation and optimizing the microstructure. However, the synergistic effects between these process parameters, layer thickness, and feedstock attributes (e.g. powder size distribution) on part characteristics such as microstructure, density, hardness, and surface roughness are not as well-studied. In this work, we investigate 316L stainless steel density cubes built via laser powder bed fusion (L-PBF), emphasizing the significant microstructural changes that occur due to altering the volumetric energy density (VED) via laser power, scan speed, and layer thickness changes, coupled with different starting powder size distributions. This study demonstrates that there is not one ideal process set and powder size distribution for each machine. Instead, there are several combinations or feedstock/process parameter ‘recipes’ to achieve similar goals. This study also establishes that for equivalent VEDs, changing powder size can significantly alter part density, GND density, and hardness. Through proper parameter and feedstock control, part attributes such as density, grain size, texture, dislocation density, hardness, and surface roughness can be customized, thereby creating multiple high-performance regions in the AM process space.

316L stainless steel↗
NASA NTRS1989

Minimum weight design of helicopter rotor blades with frequency constraints

The minimum weight design of helicopter rotor blades subject to constraints on fundamental coupled flap-lag natural frequencies has been studied in this paper. A constraint has also been imposed on the minimum value of the blade autorotational inertia to ensure that the blade has sufficient inertia to autorotate in case of an engine failure. The program CAMRAD has been used for the blade modal analysis and the program CONMIN has been used for the optimization. In addition, a linear approximation analysis involving Taylor series expansion has been used to reduce the analysis effort. The procedure contains a sensitivity analysis which consists of analytical derivatives of the objective function and the autorotational inertia constraint and central finite difference derivatives of the frequency constraints. Optimum designs have been obtained for blades in vacuum with both rectangular and tapered box beam structures. Design variables include taper ratio, nonstructural segment weights and box beam dimensions. The paper shows that even when starting with an acceptable baseline design, a significant amount of weight reduction is possible while satisfying all the constraints for blades with rectangular and tapered box beams.

Chattopadhyay, Aditi↗
DOE OSTI2023

G 0 W 0 Ionization Potentials of First-Row Transition Metal Aqua Ions

Here, we report computations of the vertical ionization potentials within the GW approximation of the near-complete series of first-row transition metal (V–Cu) aqua ions in their most common oxidation states, i.e., V 3+ , Cr 3+ , Cr 2+ , Mn 2+ , Fe 3+ , Fe 2+ , Co 2+ , Ni 2+ , and Cu 2+ . The d-orbital occupancy of these systems spans a broad range from d 2 to d 9 . All of the structures were first optimized at the density functional theory level using a large cluster of explicit water molecules that are embedded in a continuum solvation model. Vertical ionization potentials were computed with the one-shot G 0 W 0 approach on a range of transition metal ion clusters (6, 18, 40, and 60 explicit water molecules), wherein the convergence with respect to the basis set size was evaluated using the systems with 40 water molecules. We assess the results using three different density functional approximations as starting points for the vertical ionization potential calculations, namely, G 0 W 0 @PBE, G 0 W 0 @PBE0, and G 0 W 0 @r 2 SCAN. While the predicted ground-state structures are similar to all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with experiment when using the G 0 W 0 @PBE0 and G 0 W 0 @r 2 SCAN approaches, with the r 2 SCAN-based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures are in good agreement with available experimental data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗