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

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At least 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Identifying dark matter interactions in monojet searches

We study the discrimination of quark-initiated jets from gluon-initiated jets in monojet searches for dark matter using the technique of averaged jet energy profiles. We demonstrate our results in the context of effective field theories of dark matter interactions with quarks and gluons, but our methods apply more generally to a wide class of models. Different effective theories of dark matter and the standard model backgrounds each have a characteristic quark/gluon fraction for the leading jet. When used in conjunction with the traditional cut-and-count monojet search, the jet energy profile can be used to set stronger bounds on contact interactions of dark matter. In the event of a discovery of a monojet excess at the 14 TeV LHC, contact interactions between dark matter with quarks or with gluons can be differentiated at the 95% confidence level. For a given rate at the LHC, signal predictions at direct detection experiments for different dark matter interactions can span five orders of magnitude. Lastly, the ability to identify these interactions allows us to make a tighter connection between LHC searches and direct detection experiments.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Sequential Bond Dissociation Energies of Th + (CO) x , x = 3–6: Guided Ion Beam Collision-Induced Dissociation and Quantum Computational Studies

Collision-induced dissociation (CID) of [Th,xC,xO] + , x = 3–6, with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). Products are formed exclusively by the loss of CO ligands. Analyses of the kinetic energy-dependent CID product cross sections yield bond dissociation energies (BDEs) of (CO) x–1 Th + –CO at 0 K as 1.09 ± 0.05, 0.82 ± 0.07, 0.63 ± 0.05, and 0.70 ± 0.05 eV, respectively. Different structures of [Th,xC,xO] + were explored using various electronic structure methods, and BDEs for CO ligand loss from precursor [Th,xC,xO] + complexes were computed. Both experimental and theoretical results corroborate that the structures of [Th,xC,xO] + , x = 3–6, formed experimentally are homoleptic thorium cation carbonyl complexes, Th + (CO) x . The nonmonotonic trend in experimental BDEs is reproduced theoretically, although ambiguities in the spin states of the x = 4–6 complexes (doublet or quartet) remain. BDEs calculated at the coupled cluster with single, double, and perturbative triple excitations (CCSD(T))/cc-pVXZ//B3LYP/cc-PVXZ (X = T and Q) level and a complete basis set (CBS) extrapolation agree reasonably well with the experimental values for all complexes. Thorium oxide ketenylidene carbonyl cations, OTh + CCO(CO) y , y = 1–4, were calculated to be the most stable structures of [Th,xC,xO] + , x = 3–6, respectively; however, these are not observed in our experiment. Potential energy profiles (PEPs) having either quartet or doublet spin calculated at the B3LYP/cc-pVQZ level suggest that the failure to observe OTh + CCO(CO) y , y = 1–4, is the result of a barrier corresponding to the C–C bond formation, making the formation of OTh + CCO(CO) y inaccessible kinetically under the present experimental conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Model validation for inferred hot-spot conditions in National Ignition Facility experiments

Progress toward ignition requires accurately diagnosing current conditions and assessing proximity metrics for implosion experiments on the National Ignition Facility. Hot-spot conditions are not directly measured, but rather inferred, often using simple 0- and 1D models [P. Patel et al., Phys. Plasmas 27, 050901 (2020)]. In this work, we present a detailed accuracy validation exercise using a set of ~20,000 2D simulations encompassing a variety of performance and degradation levels. We find good agreement between the model-inferred pressure and the simulated burn-weighted pressure at peak neutron production and also present results on the precision of inferred quantities using a Markov-Chain Monte Carlo algorithm.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Study of the impact of resonant magnetic perturbation fields on gross tungsten erosion using DiMES samples in DIII-D

Here, an experiment was conducted in DIII-D to compare gross tungsten (W) erosion on samples exposed to outer strike point (OSP) sweeps in L-mode plasmas for three conditions. These included two phases of resonant magnetic perturbations (RMPs), and a set with no perturbations. Upon RMP application, lobe structures indicative of strike point splitting of the OSP were evident in divertor camera data and on Langmuir probes. Gross W erosion flux, ${{\rm{\Gamma }}}_{{\rm{W}}},$ inferred spectroscopically using the S/XB method applied to the 400.9 nm W-I line, was generally in the range ${{\rm{\Gamma }}}_{{\rm{W}}}/{{\rm{\Gamma }}}_{{\rm{D}}+,\perp }=2\times {10}^{-4}$ referenced to incident deuterium ion flux ${{\rm{\Gamma }}}_{{\rm{D}}+,\perp },$ and was increased in the RMP cases by no more than 30% of the level observed in unperturbed discharges. A large reduction in gross erosion (50%) was observed in the private flux region at the W sample for one specific toroidal phase of the RMP field.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Combining diagnostics, modeling, and control systems for automated alignment of the TES beamline

X-ray beamlines are essential components of all synchrotron light sources. Practical operations involve frequent variation in beamline component positions and orientation, particularly when photon beam parameters shift due to experimental needs, or due to variations in the incoming photon beam. The alignment process can be time consuming and takes away from valuable beam time for experimental data collection. We describe progress in the automation of certain alignment tasks on the tender-energy X-ray spectroscopy (TES) beamline at the National Synchrotron Light Source II (NSLS-II). The beamline is controlled using the BlueSky software in which high level experimental plans guide the beamline components during an experiment. Numerous software packages exist for beamline modeling, and they may be tied to the beamline control system using a package we are continuing to develop called Sirepo-Bluesky. The photon beam distribution may be measured with fluorescent screens, and a relation between beam and machine state can be found by varying the mirror and aperture settings over a multi-dimensional range. We describe the results of such parameter varying measurements and how we are combining Sirepo-Bluesky with machine learning methods and reduced models to automate mirror alignment on the TES beamline.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Enhancing Photosynthesis Simulation Performance in ESMs with Machine Learning-Assisted Solvers

When simulating vegetation dynamics, photosynthesis accounts for a large fraction of the computational cost in most Earth System Models (ESMs). This is largely since photosynthesis is represented as a system of nonlinear equations, and the solution requires the use of an initial guess followed by many iterations of the numerical solver to obtain a solution. We use machine learning (ML) to replicate the response surface of the model’s numerical solver to improve the choice of initial guess, therefore requiring fewer iterations to obtain a final solution. We implemented this test on the leaf-level calculations as well as at the canopy scale, and for both we observed fewer iterations of the photosynthesis solver when a ML-based initial guess was implemented. The model tested here is the Energy Exascale Earth System Model - Land Model (ELM). The ML-based algorithms used here are trained on simulations from the model itself and used only to improve the initial guess for the solver; therefore, the model maintains its own set of physics to obtain the final solution. This work shows novel ways to utilize ML-based methods to improve the performance of numerical solvers in ESMs.

Massoud, Elias [ORNL] (ORCID:0000000217725361)↗
DOE OSTI2024

Verification of Adaptive Protection in Hardware in the Loop for Coordination with Solar Variability

As inverter-based resources continue to be installed at all levels of the electric grid, the fixed protection schemes used at the distribution level will continue to be stressed until they no longer ensure the protection of the grid. Adaptive protection has been proposed as a solution with the ability to update the protection schemes in near real-time to ensure reliability and increase the resilience of the grid. However, weather variability poses a significant challenge to the ability of these methods to keep the selectivity and reliability of these schemes coordinated. If the ramp rates, due to solar variability, of the inverter-based resources change faster than the adaptive protection can issue new settings, the protection system could be uncoordinated, with the wrong device responding to a system fault. The proposed adaptive protection method ensures that due to solar variability, communication, and protection calculation latency, it can issu e coordinated protection settings promptly, in one minute or less. The hardware-in-the-loop results show the protection settings being issued and maintaining system coordination in under a minute.

Summers, Adam↗
DOE OSTI2017

Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials

An approach based on vibrational spectral measurements is described for determining the ionizable group content of ion conducting polymer membrane materials. Aimed at supporting the assessment of membrane stability and wear characteristics, performance is evaluated for attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy, confocal Raman microscopy, and ATR FT-IR microscopy using perfluorinated ionomer membrane standards. One set of ionomer standards contained a sulfonic acid ionizable group and the other a sulfonyl imide group. The average number of backbone tetrafluoroethylene (TFE) units separating the ionizable-group containing side chains was in the range of 7.2–2.1 (sulfonic acid set) and 10.5–4.6 (sulfonyl imide set). A poly(tetrafluoroethylene) (PTFE) sample was included as a blank, representing the limit of zero ionizable group (and maximum TFE) content. Calibration relationships were derived from area-normalized vibrational spectra. For all three methods, calibration models applied to independent spectral measurements of samples predicted the ratio of backbone TFE groups to ionizable groups in the repeat unit ( m) with a standard error of ≤ ±0.3. The confocal Raman and ATR FT-IR microscopy techniques achieved ideal blank responses and the lowest prediction errors, down to m ± 0.1 at the 90% confidence level. With its relative simplicity, low sample size requirements, and potential for quantitative micron-scale spatial mapping of the ionizable group content within a membrane, the approach has application to advancing materials development, including exploratory synthesis, durability and wear assessment, and in situ studies of membrane process.

Korzeniewski, Carol↗
DOE OSTI2013

Evaluation of a Turbidity Meter for Use at the Defense Waste Processing Facility

Savannah River Remediation’s (SRR’s) Defense Waste Processing Facility (DWPF) Laboratory currently tests for sludge carry-over into the Recycle Collection Tank (RCT) by evaluating the iron concentration in the Slurry Mix Evaporator Condensate Tank (SMECT) and relating this iron concentration to the amount of sludge solids present. A new method was proposed for detecting the amount of sludge in the SMECT that involves the use of an Optek turbidity sensor. Waste Services Laboratory (WSL) personnel conducted testing on two of these units following a test plan developed by Waste Solidification Engineering (WSE). Both Optek units (SN64217 and SN65164) use sensor model AF16-N and signal converter model series C4000. The sensor body of each unit was modified to hold a standard DWPF 12 cc sample vial, also known as a “peanut” vial. The purpose of this testing was to evaluate the use of this model of turbidity sensor, or meter, to provide a measurement of the sludge solids present in the SMECT based upon samples from that tank. During discussions of the results from this study by WSE, WSL, and Savannah River National Laboratory (SRNL) personnel, an upper limit on the acceptable level of solids in SMECT samples was set at 0.14 weight percent (wt%). A “go/no-go” decision criterion was to be developed for the critical turbidity response, which is expressed in concentration units (CUs), for each Optek unit based upon the 0.14 wt% solids value. An acceptable or a “go” decision for the SMECT should reflect the situation that there is an identified risk (e.g. 5%) for a CU response from the Optek unit to be less than the critical CU value when the solids content of the SMECT is actually 0.14 wt% or greater, while a “no-go” determination (i.e., an Optek CU response above the critical CU value, a conservative decision relative to risk) would lead to additional evaluations of the SMECT to better quantify the possible solids content of the tank. Subsequent to the issuance of the initial version of this report but under the scope of the original request for technical assistance, WSE asked for this report to be revised to include the “go/no-go” CU value corresponding to 0.28 wt% solids. It was this request that led to the preparation of Revision 1 of the report. The results for the 0.28 wt% solids value were developed following the same approach as that utilized for the 0.14 wt% solids value. A sludge simulant was used to develop standards for testing both Optek units and to determine the viability of a “go/no-go” CU response for each of the units. Statistical methods were used by SRNL to develop the critical CU value for the “go/no-go” decision for these standards for each Optek unit. Since only one sludge simulant was available for this testing, the sensitivity of these results to other simulants and to actual sludge material is not known. However, limited testing with samples from the actual DWPF process (both SRAT product samples and SMECT samples) demonstrated that the use of the “go/no-go” criteria developed from the sludge simulant testing was conservative for these samples taken from the sludge batch, Sludge Batch 7b, being processed at the time of this testing. While both of the Optek units performed very reliably during this testing, there were statistically significant differences (although small on a practical scale) between the two units. Thus, testing should be conducted on any new unit of this Optek model to qualify it before it is used to support the DWPF operation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Assessing thermal comfort and participation in residential demand flexibility programs

Residential space-conditioning-based demand flexibility (DF) has become an increasingly sought-after method for demand-side load management to enhance grid reliability and facilitate integration of renewable energy generation. However, predicting the effectiveness and flexibility of residential DF resources is challenging due to the variability in household energy use behaviors. Current estimates show that only 50 % of projected savings from DF resources are actualized due to regulatory, technological, and social barriers. From a household perspective, concerns over thermal comfort during space conditioning-based DF events significantly impact participation decisions. Currently, there is a very limited understanding of how thermal comfort during space-conditioning-based DF events in real-world settings impacts household energy use behaviors and, consequently, the success of DF programs in achieving targeted savings. This paper proposes a method to comprehensively assess the thermal comfort implications of DF strategies and presents results of their impacts on DF event participation decisions and demand savings. Here, the proposed method was applied to a heat pump DF field study in Cordova, Alaska. The study’s key findings are: 1) DF event setpoint offsets that maintain indoor operative temperatures between 18 to 22 °C (65 to 71°F) may be preferred in Cordova, Alaska; 2) Household-level thermal comfort is more sensitive to the duration of the DF event than to the degree of temperature offset from baseline conditions; 3) The delayed impact of changes in indoor operative temperature in response to setpoint offsets, both during and after a DF event, influences occupants’ thermal comfort perceptions and willingness to persistently participate in events. The findings from application of the proposed method can help inform future larger-scale occupant-centric DF programs as it can capture information not readily available through utility and device-level energy use data. Thus, it can supplement these sources and help program administrators develop occupant-centric DF strategies, enabling more accurate predictions of participation rates and savings estimates for space-conditioning-based DF programs.

Demand side management↗
DOE OSTI2015

Big Data Meets Quantum Chemistry Approximations: The Δ-Machine Learning Approach

Chemically accurate and comprehensive studies of the virtual space of all possible molecules are severely limited by the computational cost of quantum chemistry. Here we introduce a composite strategy that adds machine learning corrections to computationally inexpensive approximate legacy quantum methods. After training, highly accurate predictions of enthalpies, free energies, entropies, and electron correlation energies are possible, for significantly larger molecular sets than used for training. For thermochemical properties of up to 16k isomers of C 7 H 10 O 2 we present numerical evidence that chemical accuracy can be reached. We also predict electron correlation energy in post Hartree-Fock methods, at the computational cost of HartreeFock, and we establish a qualitative relationship between molecular entropy and electron correlation. The transferability of our approach is demonstrated, using semiempirical quantum chemistry and machine learning models trained on 1 and 10% of 134k organic molecules, to reproduce enthalpies of all remaining molecules at density functional theory level of accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A static quantum embedding scheme based on coupled cluster theory

Here, we develop a static quantum embedding scheme that utilizes different levels of approximations to coupled cluster (CC) theory for an active fragment region and its environment. To reduce the computational cost, we solve the local fragment problem using a high-level CC method and address the environment problem with a lower-level Møller–Plesset (MP) perturbative method. This embedding approach inherits many conceptual developments from the hybrid second-order Møller–Plesset (MP2) and CC works by Nooijen [J. Chem. Phys. 111, 10815 (1999)] and Bochevarov and Sherrill [J. Chem. Phys. 122, 234110 (2005)]. We go beyond those works here by primarily targeting a specific localized fragment of a molecule and also introducing an alternative mechanism to relax the environment within this framework. We will call this approach MP-CC. We demonstrate the effectiveness of MP-CC on several potential energy curves and a set of thermochemical reaction energies, using CC with singles and doubles as the fragment solver, and MP2-like treatments of the environment. The results are substantially improved by the inclusion of orbital relaxation in the environment. Using localized bonds as the active fragment, we also report results for N=N bond breaking in azomethane and for the central C–C bond torsion in butadiene. We find that when the fragment Hilbert space size remains fixed (e.g., when determined by an intrinsic atomic orbital approach), the method achieves comparable accuracy with both a small and a large basis set. Additionally, our results indicate that increasing the fragment Hilbert space size systematically enhances the accuracy of observables, approaching the precision of the full CC solver.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Resilience Design Patterns - A Structured Approach to Resilience at Extreme Scale (version 1.1)

Reliability is a serious concern for future extreme-scale high-performance computing (HPC) systems. Projections based on the current generation of HPC systems and technology roadmaps suggest the prevalence of very high fault rates in future systems. The errors resulting from these faults will propagate and generate various kinds of failures, which may result in outcomes ranging from result corruptions to catastrophic application crashes. Therefore the resilience challenge for extreme-scale HPC systems requires management of various hardware and software technologies that are capable of handling a broad set of fault models at accelerated fault rates. Also, due to practical limits on power consumption in HPC systems future systems are likely to embrace innovative architectures, increasing the levels of hardware and software complexities. As a result the techniques that seek to improve resilience must navigate the complex trade-off space between resilience and the overheads to power consumption and performance. While the HPC community has developed various resilience solutions, application-level techniques as well as system-based solutions, the solution space of HPC resilience techniques remains fragmented. There are no formal methods and metrics to investigate and evaluate resilience holistically in HPC systems that consider impact scope, handling coverage, and performance & power efficiency across the system stack. Additionally, few of the current approaches are portable to newer architectures and software environments that will be deployed on future systems. In this document, we develop a structured approach to the management of HPC resilience using the concept of resilience-based design patterns. A design pattern is a general repeatable solution to a commonly occurring problem. We identify the commonly occurring problems and solutions used to deal with faults, errors and failures in HPC systems. Each established solution is described in the form of a pattern that addresses concrete problems in the design of resilient systems. The complete catalog of resilience design patterns provides designers with reusable design elements. We also define a framework that enhances a designer's understanding of the important constraints and opportunities for the design patterns to be implemented and deployed at various layers of the system stack. This design framework may be used to establish mechanisms and interfaces to coordinate flexible fault management across hardware and software components. The framework also supports optimization of the cost-benefit trade-offs among performance, resilience, and power consumption. The overall goal of this work is to enable a systematic methodology for the design and evaluation of resilience technologies in extreme-scale HPC systems that keep scientific applications running to a correct solution in a timely and cost-efficient manner in spite of frequent faults, errors, and failures of various types.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Reference document for LANL stack sampling and ANSI N13.1 (Article) Gielow RL and McNamee MR 1993. Numerical Flue Gas Flow Modeling for Continuous Emissions Monitoring Applications. EPRI CEM Users Group Meeting. Baltimore. RP1961-13

American National Standard N13.1 “sets forth guidelines and performance criteria for sampling the emissions of airborne radioactive substances in the air discharge ducts and stacks of nuclear facilities. Emphasis is on extractive sampling from a location in a stack or duct where the contaminant is well mixed. At such a location, sampling may be conducted at a single point. This standard provides performance-based criteria for the use of air sampling probes, transport lines, sample collectors, sample monitoring instruments, and gas flow measuring methods. This standard also covers sampling program objectives, quality assurance issues, developing air sampling action levels, system optimization, and system performance verification. Workplace, containment, and environmental air monitoring are not addressed. Specific sample analysis methods and the reporting or interpreting of results are also not addressed.” (HPS 2011).

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2024

Engineered living materials for capture, conversion, and recycling technologies

Continued dependence on crude oil and natural gas resources for fossil fuels has caused global atmospheric carbon dioxide (CO 2 ) emissions to increase to record-setting proportions. There is an urgent need for efficient and inexpensive carbon sequestration systems to mitigate large-scale CO 2 emissions from industrial flue gas. Carbonic anhydrase (CA) has shown high potential for enhanced CO 2 capture applications compared to conventional absorption-based methods currently utilized in various industrial settings. This study aims to understand structural aspects that contribute to the stability of CA enzymes critical for their applications in industrial processes, which require the ability to withstand conditions different from their native environments. Here, we evaluated the thermostability and enzyme activity of mesophilic and thermophilic CA variants at different temperature conditions and in the presence of atmospheric gas pollutants like nitrogen oxides (NO x ) and sulphur oxides (SO x ). Based on our enzyme activity assays and molecular dynamics simulations, we see increased conformational stability and CA activity levels in thermostable CA variants incubated week-long at different temperature conditions. The thermostable CA variants also retained high levels of CA activity despite changes in solution pH due to increasing NO x and SO x concentrations. Furthermore, a loss of CA activity was observed only at high concentrations of NO x /SO x that possibly can be minimized with appropriate buffered solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

First M87 Event Horizon Telescope Results. VII. Polarization of the Ring

In 2017 April, the Event Horizon Telescope (EHT) observed the near-horizon region around the supermassive black hole at the core of the M87 galaxy. These 1.3 mm wavelength observations revealed a compact asymmetric ring-like source morphology. This structure originates from synchrotron emission produced by relativistic plasma located in the immediate vicinity of the black hole. Here we present the corresponding linear-polarimetric EHT images of the center of M87. We find that only a part of the ring is significantly polarized. The resolved fractional linear polarization has a maximum located in the southwest part of the ring, where it rises to the level of ~15%. The polarization position angles are arranged in a nearly azimuthal pattern. We perform quantitative measurements of relevant polarimetric properties of the compact emission and find evidence for the temporal evolution of the polarized source structure over one week of EHT observations. The details of the polarimetric data reduction and calibration methodology are provided. We carry out the data analysis using multiple independent imaging and modeling techniques, each of which is validated against a suite of synthetic data sets. The gross polarimetric structure and its apparent evolution with time are insensitive to the method used to reconstruct the image. These polarimetric images carry information about the structure of the magnetic fields responsible for the synchrotron emission. Their physical interpretation is discussed in an accompanying publication.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Protoplanetary Disk Masses from Radiative Transfer Modeling: A Case Study in Taurus

Measuring the masses of protoplanetary disks is crucial for understanding their planet-forming potential. Typically, dust masses are derived from (sub-)millimeter flux density measurements plus assumptions for the opacity, temperature, and optical depth of the dust. Here we use radiative transfer models to quantify the validity of these assumptions with the aim of improving the accuracy of disk dust mass measurements. We first carry out a controlled exploration of disk parameter space. We find that the disk temperature is a strong function of disk size, while the optical depth depends on both disk size and dust mass. The millimeter-wavelength spectral index can be significantly shallower than the naive expectation due to a combination of optical depth and deviations from the Rayleigh–Jeans regime. We fit radiative transfer models to the spectral energy distributions (SEDs) of 132 disks in the Taurus-Auriga region using a Markov chain Monte Carlo approach. We used all available data to produce the most complete SEDs used in any extant modeling study. We perform the fitting twice: first with unconstrained disk sizes and again imposing the disk size–brightness relation inferred for sources in Taurus. This constraint generally forces the disks to be smaller, warmer, and more optically thick. From both sets of fits, we find disks to be ∼1–5 times more massive than when derived using (sub-)millimeter measurements and common assumptions. With the uncertainties derived from our model fitting, the previously measured dust mass–stellar mass correlation is present in our study but only significant at the 2σ level.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Evaluating fast methods for static polarizabilities on extended conjugated oligomers

Given the importance of accurate polarizability calculations to many chemical applications, coupled with the need for efficiency when calculating the properties of sets of molecules or large oligomers, we present a benchmark study examining possible calculation methods for polarizable materials. We first investigate the accuracy of the additive model used in GFN2, a highly-efficient semi-empirical tight-binding method, and the D4 dispersion model, comparing its predicted additive polarizabilities to ωB97XD results for a subset of PubChemQC and a compiled benchmark set of molecules spanning polarizabilities from approximately 3 Å 3 to 600 Å 3 , with some compounds in the range of approximately 1200–1400 Å 3 . Although we find additive GFN2 polarizabilities, and thus D4, to have large errors with polarizability calculations on large conjugated oligomers, it would appear an empirical quadratic correction can largely remedy this. We also compare the accuracy of DFT polarizability calculations run using basis sets of varying size and level of augmentation, determining that a non-augmented basis set may be used for large, highly polarizable species in conjunction with a linear correction factor to achieve accuracy extremely close to that of aug-cc-pVTZ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗