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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Distance-Decay Relationship for Biological Wastewater Treatment Plants

Patterns in the spatial distribution of organisms provide important information about mechanisms underlying biodiversity and the complexity of ecosystems. One of the most well-documented spatial patterns is the distance-decay relationship, which is a universal biogeographic pattern observed repeatedly for plant and animal communities, particularly for microorganisms in natural ecosystems such as soil, ocean, and salt marsh sediment. However, it is uncertain whether the microorganisms exhibit a distance-decay pattern in engineered ecosystems. Therefore, we measured the distance-decay relationship across various microbial functional and phylogenetic groups in 26 biological wastewater treatment plants (WWTPs) in China using a functional gene array (GeoChip 4.2). We found that microbial communities of activated sludge in WWTPs exhibited a significant but very weak distance-decay relationship. The taxon-area z values for different functional and phylogenetic groups were <0.0065, which is about 1 to 2 orders of magnitude lower than those observed in microbial communities elsewhere. Variation-partitioning analysis (VPA) showed that the relationships were driven by both environmental heterogeneity and geographic distance. Collectively, these results provided new insights into the spatial scaling of microbial communities in engineering ecosystems and highlighted the importance of environmental heterogeneity and geographic distance in shaping biogeographic patterns.Determining the distance-decay relationship of microbial biodiversity is important but challenging in microbial ecology. All studies to date are based on natural environments; thus, it remains unclear whether there is such a relationship in an engineered ecosystem. The present study shows that there is a very weak distance-decay relationship in an engineered ecosystem (WWTPs) at the regional-to-continental scale. This study makes fundamental contributions to a mechanistic, predictive understanding of microbial biogeography.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

From individual leaves to forest stands: importance of niche, distance decay, and stochasticity vary by ecosystem type and functional group for fungal community composition

Abstract Community assembly is influenced by environmental niche processes as well as stochastic processes that can be spatially dependent (e.g. dispersal limitation) or independent (e.g. priority effects). Here, we sampled senesced tree leaves as unit habitats to investigate fungal community assembly at two spatial scales: (i) small neighborhoods of overlapping leaves from differing tree species and (ii) forest stands of differing ecosystem types. Among forest stands, ecosystem type explained the most variation in community composition. Among adjacent leaves within stands, variability in fungal composition was surprisingly high. Leaf type was more important in stands with high soil fertility and dominated by differing tree mycorrhizal types (sugar maple vs. basswood or red oak), whereas distance decay was more important in oak-dominated forest stands with low soil fertility. Abundance of functional groups was explained by environmental factors, but predictors of taxonomic composition within differing functional groups were highly variable. These results suggest that fungal community assembly processes are clearest for functional group abundances and large spatial scales. Understanding fungal community assembly at smaller spatial scales will benefit from further study focusing on differences in drivers for different ecosystems and functional groups, as well as the importance of spatially independent factors such as priority effects.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Long-distance decay-less spin transport in indirect excitons in a van der Waals heterostructure

AbstractIn addition to its fundamental interest, the long-distance spin transport is essential for spintronic devices. However, the spin relaxation caused by scattering of the particles carrying the spin limits spin transport. We explored spatially indirect excitons (IXs) in van der Waals heterostructures composed of atomically thin layers of transition-metal dichalcogenides as spin carries. We observed the long-distance spin transport: the spin polarized excitons travel over the entire sample, ~10 micron away from the excitation spot, with no spin density decay. This transport is characterized by the 1/e decay distances reaching ~100 micron. The 1/e decay distances are extracted from fits over the ~10 micron sample size. The emergence of long-distance spin transport is observed at the densities and temperatures where the IX transport decay distances and, in turn, scattering times are strongly enhanced. The suppression of IX scattering suppresses the spin relaxation and enables the long-distance spin transport.

Science & Technology - Other Topics↗
NASA NTRS2000

Transverse Stress Decay in a Specially Orthotropic Strip Under Localizing Normal Edge Loading

Solutions are presented for the stresses in a specially orthotropic infinite strip which is subjected to localized uniform normal loading on one edge while the other edge is either restrained against normal displacement only, or completely fixed. The solutions are used to investigate the diffusion of load into the strip and in particular the decay of normal stress across the width of the strip. For orthotropic strips representative of a broad range of balanced and symmetric angle-ply composite laminates, minimum strip widths are found that ensure at least 90% decay of the normal stress across the strip. In addition, in a few cases where, on the fixed edge the peak shear stress exceeds the normal stress in magnitude, minimum strip widths that ensure 90% decay of both stresses are found. To help in putting these results into perspective, and to illustrate the influence of material properties on load 9 orthotropic materials, closed-form solutions for the stresses in similarly loaded orthotropic half-planes are obtained. These solutions are used to generate illustrative stress contour plots for several representative laminates. Among the laminates, those composed of intermediate-angle plies, i.e., from about 30 degrees to 60 degrees, exhibit marked changes in normal stress contour shape with stress level. The stress contours are also used to find 90% decay distances in the half-planes. In all cases, the minimum strip widths for 90% decay of the normal stress exceed the 90% decay distances in the corresponding half-planes, in amounts ranging from only a few percent to about 50% of the half-plane decay distances. The 90% decay distances depend on both material properties and the boundary conditions on the supported edge.

Fichter, W. B.↗
DOE OSTI2019

The spatial scale dependence of diazotrophic and bacterial community assembly in paddy soil

Aim: The factors driving microbial community β-diversity (variation in composition) at different spatial scales yield fundamental insights into the mechanisms that maintain ecosystem biodiversity, which as yet are uncertain. In this work, we explore whether spatial scale-dependent patterns of β-diversity vary between microbial functional groups and bacterial taxa (i.e., diazotrophic and bacterial communities) across local to regional scales (from metres to hundreds of kilometres). Location: Eastern China. Time period: October and November 2015. Major taxa studied: Diazotrophic and bacterial communities. Methods: We use two complementary statistical tools to unveil biotic mechanisms (i.e., species association) underlying variation in β-diversity of diazotrophic and bacterial communities. We examined distance–decay slopes of both communities at the local (1–113 m), meso- (3.4–39 km) and regional (103–668 km) scales. We used an environmentally constrained checkerboard score and topological features of association networks as indices of species association. We then calculated contributions of species association, abiotic factors and geographical distance to explain community β-diversity. The scale-dependent distance–decay relationships were also examined in ubiquitous (high occupancy across samples) and endemic communities of diazotrophs and bacteria. Results: Diazotrophs displayed steeper distance–decay slopes than bacteria, suggesting that the β-diversity of diazotrophic communities was more variable. The distance–decay slopes were dependent on spatial scales in both communities, owing to different contributions of geographical distance, abiotic factors and species association at three spatial scales. Intriguingly, species association was greater and contributed more to community β-diversity than other forces at the local scale, implying that species association could greatly alter community structures. Main conclusions: Drivers of diazotrophic and bacterial community β-diversity depended on spatial scales, resulting in different distance–decay patterns. Moreover, this was the first study to use two methods to demonstrate that species association played important, but as yet unrecognized, roles in driving spatial scale-dependent β-diversity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Habitat-specific patterns and drivers of bacterial β-diversity in China’s drylands

The existence of biogeographic patterns among most free-living microbial taxa has been well established, yet little is known about the underlying mechanisms that shape these patterns. In this work, we examined soil bacterial β-diversity across different habitats in the drylands of northern China. We evaluated the relative importance of environmental factors versus geographic distance to a distance-decay relationship, which would be explained by the relative effect of basic ecological processes recognized as drivers of diversity patterns in macrobial theoretical models such as selection and dispersal. While the similarity of bacterial communities significantly declined with increasing geographic distance, the distance-decay slope and the relative importance of factors driving distance-decay patterns varied across different habitats. A strong distance-decay relationship was observed in the alpine grassland, where the community similarity was influenced only by the environmental factors. Yet, geographic distance was solely responsible for community similarity in the desert. Even the average compositional similarity among locations in the desert was distinctly lower compared with those in other habitats. We found no evidence that dispersal limitation strongly influenced the β-diversity of bacterial communities in the desert grassland and typical grassland. Together, our results provide robust evidence of habitat specificity for microbial diversity patterns and their underlying drivers. Our findings suggest that microorganisms also have multiple drivers of diversity patterns and some of which may be parallel to some fundamental processes for explaining biodiversity patterns in macroorganisms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Distinct Biogeographic Patterns for Archaea, Bacteria, and Fungi along the Vegetation Gradient at the Continental Scale in Eastern China

Understanding biogeographic patterns is a precursor to improving our knowledge of the function of microbiomes and to predicting ecosystem responses to environmental change. Using natural forest soil samples from 110 locations, this study is one of the largest attempts to comprehensively understand the different patterns of soil archaeal, bacterial, and fungal biogeography at the continental scale in eastern China. These patterns in natural forest sites could ascertain reliable soil microbial biogeographic patterns by eliminating anthropogenic influences. This information provides guidelines for monitoring the belowground ecosystem’s decline and restoration. Meanwhile, the deviations in the soil microbial communities from corresponding natural forest states indicate the extent of degradation of the soil ecosystem. Moreover, given the association between vegetation type and the microbial community, this information could be used to predict the long-term response of the underground ecosystem to the vegetation distribution caused by global climate change. The natural forest ecosystem in Eastern China, from tropical forest to boreal forest, has declined due to cropland development during the last 300 years, yet little is known about the historical biogeographic patterns and driving processes for the major domains of microorganisms along this continental-scale natural vegetation gradient. We predicted the biogeographic patterns of soil archaeal, bacterial, and fungal communities across 110 natural forest sites along a transect across four vegetation zones in Eastern China. The distance decay relationships demonstrated the distinct biogeographic patterns of archaeal, bacterial, and fungal communities. While historical processes mainly influenced bacterial community variations, spatially autocorrelated environmental variables mainly influenced the fungal community. Archaea did not display a distance decay pattern along the vegetation gradient. Bacterial community diversity and structure were correlated with the ratio of acid oxalate-soluble Fe to free Fe oxides (Feo/Fed ratio). Fungal community diversity and structure were influenced by dissolved organic carbon (DOC) and free aluminum (Ald), respectively. The role of these environmental variables was confirmed by the correlations between dominant operational taxonomic units (OTUs) and edaphic variables. However, most of the dominant OTUs were not correlated with the major driving variables for the entire communities. These results demonstrate that soil archaea, bacteria, and fungi have different biogeographic patterns and driving processes along this continental-scale natural vegetation gradient, implying different community assembly mechanisms and ecological functions for archaea, bacteria, and fungi in soil ecosystems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The role of geography in the complex diffusion of innovations

The urban–rural divide is increasing in modern societies calling for geographical extensions of social influence modelling. Improved understanding of innovation diffusion across locations and through social connections can provide us with new insights into the spread of information, technological progress and economic development. In this work, we analyze the spatial adoption dynamics of iWiW, an Online Social Network (OSN) in Hungary and uncover empirical features about the spatial adoption in social networks. During its entire life cycle from 2002 to 2012, iWiW reached up to 300 million friendship ties of 3 million users. We find that the number of adopters as a function of town population follows a scaling law that reveals a strongly concentrated early adoption in large towns and a less concentrated late adoption. We also discover a strengthening distance decay of spread over the life-cycle indicating high fraction of distant diffusion in early stages but the dominance of local diffusion in late stages. The spreading process is modelled within the Bass diffusion framework that enables us to compare the differential equation version with an agent-based version of the model run on the empirical network. Although both model versions can capture the macro trend of adoption, they have limited capacity to describe the observed trends of urban scaling and distance decay. We find, however that incorporating adoption thresholds, defined by the fraction of social connections that adopt a technology before the individual adopts, improves the network model fit to the urban scaling of early adopters. Controlling for the threshold distribution enables us to eliminate the bias induced by local network structure on predicting local adoption peaks. Finally, we show that geographical features such as distance from the innovation origin and town size influence prediction of adoption peak at local scales in all model specifications.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Spatial turnover of soil viral populations and genotypes overlain by cohesive responses to moisture in grasslands

Viruses shape microbial communities, food web dynamics, and carbon and nutrient cycling in diverse ecosystems. However, little is known about the patterns and drivers of viral community composition, particularly in soil, precluding a predictive understanding of viral impacts on terrestrial habitats. To investigate soil viral community assembly processes, here we analyzed 43 soil viromes from a rainfall manipulation experiment in a Mediterranean grassland in California. We identified 5,315 viral populations (viral operational taxonomic units [vOTUs] with a representative sequence ≥10 kbp) and found that viral community composition exhibited a highly significant distance–decay relationship within the 200-m 2 field site. This pattern was recapitulated by the intrapopulation microheterogeneity trends of prevalent vOTUs (detected in ≥90% of the viromes), which tended to exhibit negative correlations between spatial distance and the genomic similarity of their predominant allelic variants. Although significant spatial structuring was also observed in the bacterial and archaeal communities, the signal was dampened relative to the viromes, suggesting differences in local assembly drivers for viruses and prokaryotes and/or differences in the temporal scales captured by viromes and total DNA. Despite the overwhelming spatial signal, evidence for environmental filtering was revealed in a protein-sharing network analysis, wherein a group of related vOTUs predicted to infect actinobacteria was shown to be significantly enriched in low-moisture samples distributed throughout the field. Overall, our results indicate a highly diverse, dynamic, active, and spatially structured soil virosphere capable of rapid responses to changing environmental conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Diazotrophs Show Signs of Restoration in Amazon Rain Forest Soils with Ecosystem Rehabilitation

Biological nitrogen fixation can be an important source of nitrogen in tropical forests that serve as a major CO 2 sink. Extensive deforestation of the Amazon is known to influence microbial communities and the biogeochemical cycles they mediate. However, it is unknown how diazotrophs (nitrogen-fixing microorganisms) respond to deforestation and subsequent ecosystem conversion to agriculture, as well as whether they can recover in secondary forests that are established after agriculture is abandoned. To address these knowledge gaps, here we combined a spatially explicit sampling approach with high-throughput sequencing of nifH genes. The main objectives were to assess the functional distance decay relationship of the diazotrophic bacterial community in a tropical forest ecosystem and to quantify the roles of various factors that drive the observed changes in the diazotrophic community structure. We observed an increase in local diazotrophic diversity (α-diversity) with a decrease in community turnover (β-diversity), associated with a shift in diazotrophic community structure as a result of the forest-to-pasture conversion. Both diazotrophic community turnover and structure showed signs of recovery in secondary forests. Changes in the diazotrophic community were primarily driven by the change in land use rather than differences in geochemical characteristics or geographic distances. The diazotroph communities in secondary forests resembled those in primary forests, suggesting that at least partial recovery of diazotrophs is possible following agricultural abandonment. IMPORTANCE The Amazon region is a major tropical forest region that is being deforested at an alarming rate to create space for cattle ranching and agriculture. Diazotrophs (nitrogen-fixing microorganisms) play an important role in supplying soil N for plant growth in tropical forests. It is unknown how diazotrophs respond to deforestation and whether they can recover in secondary forests that establish after agriculture is abandoned. Using high-throughput sequencing of nifH genes, we characterized the response of diazotrophs’ β-diversity and identified major drivers of changes in diazotrophs from forest-to-pasture and pasture-to-secondary-forest conversions. Studying the impact of land use change on diazotrophs is important for a better understanding of the impact of deforestation on tropical forest ecosystem functioning, and our results on the potential recovery of diazotrophs in secondary forests imply the possible restoration of ecosystem functions in secondary forests.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

Neutrino decays over cosmological distances and the implications for neutrino telescopes

We discuss decays of ultra-relativistic neutrinos over cosmological distances by solving the decay equation in terms of its redshift dependence. We demonstrate that there are significant conceptual differences compared to more simplified treatments of neutrino decay. For instance, the maximum distance the neutrinos have traveled is limited by the Hubble length, which means that the common belief that longer neutrino lifetimes can be probed by longer distances does not apply. As a consequence, the neutrino lifetime limit from supernova 1987A cannot be exceeded by high-energy astrophysical neutrinos. We discuss the implications for neutrino spectra and flavor ratios from gamma-ray bursts as one example of extragalactic sources, using up-to-date neutrino flux predictions. If the observation of SN 1987A implies that ν{sub 1} is stable and the other mass eigenstates decay with rates much smaller than their current bounds, the muon track rate can be substantially suppressed compared to the cascade rate in the region IceCube is most sensitive to. In this scenario, no gamma-ray burst neutrinos may be found using muon tracks even with the full scale experiment, whereas reliable information on high-energy astrophysical sources can only be obtained from cascade measurements. As another consequence, the recently observed two cascade event candidates at PeV energies will not be accompanied by corresponding muon tracks.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1982

Farfield inflight measurement of high-speed turboprop noise

A flight program was carried out to determine the variation of noise level with distance from a model high speed propeller. Noise measurements were obtained at different distances from a SR-3 propeller mounted on a JetStar aircraft, with the test instrumentation mounted on a Lear jet flown in formation. The propeller was operated at 0.8 flight Mach number, 1.12 helical tip Mach number and at 0.7 flight Mach number, 1.0 helical tip Mach number. The instantaneous pressure from individual blades was observed to rise faster at the 0.8 M flight speed, than at the 0.7 M flight speed. The measured levels appeared to decrease in good agreement with a 6 dB/doubling of distance decay, over the measurement range of approximately 16 m to 100 m distance. Further extrapolation, to the distances represented by a community, would suggest that the propagated levels during cruise would not cause a serious community annoyance.

Balombin, J. R.↗
NASA NTRS1983

Farfield inflight measurements of high-speed turboprop noise

A flight program was carried out to determine the variation of noise level with distance from a model high-speed propeller. Noise measurements were obtained at different distances from a SR-3 propeller mounted on a JetStar aircraft, with the test instrumentation mounted on a Learjet flown in formation. The propeller was operated at 0.8 m flight Mach number, 1.12 helical tip Mach number and at 0.7 flight Mach number, 1.0 helical tip Mach number. The instantaneous pressure from individual blades was observed to rise faster at the 0.8 flight speed, than at the 0.7 M flight speed. The measured levels appeared to decrease in good agreement with a 6 dB/doubling of distance decay, over the measurement range of approximately 16 m to 100 m distance. Further extrapolation, to the distances represented by a community, would suggest that the propagated levels during cruise would not cause a serious community annoyance.

Balombin, J. R.↗
NASA NTRS1980

Evaluation of a new concept for reducing free-stream turbulence in wind tunnels

A 45 deg-honeycomb flow manipulator, mounted parallel to the corner turning vanes, was investigated for improving the flow quality in wind tunnels with little or no settling chamber length. This manipulator permits increased turbulence decay distance in comparison to a conventional honeycomb arrangement. The resulting turbulence levels in a wind tunnel using the 45 deg-honeycomb are comparable to those obtained using a conventional honeycomb, but only when a 45 deg-screen is mounted immediately downstream of the honeycomb and when some separation distance between the turning vanes and the 45 deg-honeycomb is provided for adequate decay of the turning vane wakes (at least twice the spacing between the turning vanes).

Wigeland, R. A.↗
DOE OSTI2016

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Ground Motion and Intraevent Variability from 3D Deterministic Broadband (0-7.5 Hz) Simulations along a Nonplanar Strike-Slip Fault

In the article, we model deterministic broadband (-7.5 Hz) ground motion from an M w 7.1 bilateral strike-slip earthquake scenario with dynamic rupture propagation along a rough-fault topography embedded in a medium including small-scale velocity and density perturbations. Spectral accelerations (SAs) at periods 0.2-3 s and Arias intensity durations show a similar distance decay (at the level of 1-2 interevent standard deviations above the median) when compared to Next Generation Attenuation-West2 (NGA)-West2 ground-motion prediction equations (GMPEs) using a Q(f) power-law exponent of 0.6-0.8 above 1 Hz in models with a minimum V S of 750 m/s. With a trade-off from Q(f), the median ground motion is slightly increased by scattering from statistical models of small-scale heterogeneity with standard deviation (σ) of the perturbations at the lower end of the observed range (5%) but reduced by scattering attenuation at the upper end (10%) when using a realistic 3D background velocity model. The ground-motion variability is strongly affected by the addition of small-scale media heterogeneity, reducing otherwise large values of intraevent standard deviation closer to those of empirical observations. These simulations generally have intraevent standard deviations for SAs lower than the GMPEs for the modeled bandwidth, with an increasing trend with distance (most pronounced in low-to-moderate scattering media) near the level of observations at distances greater than 35 km from the fault. Durations for the models follow the same increasing trend with distance, in which σ~5% produces the best match to GMPE values. We find that a 3D background-velocity model reduces the pulse period into the expected range by breaking up coherent waves from directivity, generating a lognormal distribution of ground-motion residuals. These results indicate that a strongly heterogeneous medium is needed to produce realistic deterministic broadband ground motions. Finally, the addition of a thin surficial layer with low, frequency-independent Q in the model (with a minimum V S of 750 m/s) controls the high-frequency decay in energy, as measured by the parameter κ, that may be necessary to include as simulations continue to extend to higher frequencies.

Geochemistry & Geophysics↗
DOE OSTI2017

Casimir force phase transitions in the graphene family

The Casimir force is a universal interaction induced by electromagnetic quantum fluctuations between any types of objects. We found that the expansion of the graphene family by adding silicene, germanene and stanene (2D allotropes of Si, Ge, and Sn), lends itself as a platform to probe Dirac-like physics in honeycomb staggered systems in such a ubiquitous interaction. Here, we discover Casimir force phase transitions between these staggered 2D materials induced by the complex interplay between Dirac physics, spin-orbit coupling and externally applied fields. Particularly, we find that the interaction energy experiences different power law distance decays, magnitudes and dependences on characteristic physical constants. Furthermore, due to the topological properties of these materials, repulsive and quantized Casimir interactions become possible.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Electronic couplings for molecular charge transfer: Benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations

We introduce a database (HAB11) of electronic coupling matrix elements (H{sub ab}) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level of theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported for this database to assess the performance of three DFT methods of decreasing computational cost, including constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), and self-consistent charge density functional tight-binding (FODFTB). We find that the CDFT approach in combination with a modified PBE functional containing 50% Hartree-Fock exchange gives best results for absolute H{sub ab} values (mean relative unsigned error = 5.3%) and exponential distance decay constants β (4.3%). CDFT in combination with pure PBE overestimates couplings by 38.7% due to a too diffuse excess charge distribution, whereas the economic FODFT and highly cost-effective FODFTB methods underestimate couplings by 37.6% and 42.4%, respectively, due to neglect of interaction between donor and acceptor. The errors are systematic, however, and can be significantly reduced by applying a uniform scaling factor for each method. Applications to dimers outside the database, specifically rotated thiophene dimers and larger acenes up to pentacene, suggests that the same scaling procedure significantly improves the FODFT and FODFTB results for larger π-conjugated systems relevant to organic semiconductors and DNA.

74 ATOMIC AND MOLECULAR PHYSICS↗