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Rangeland degradation is a global concern that is exacerbated by soil loss through water erosion. A deeper understanding of rainfall and runoff dynamics can assist in the development of sustainable management strategies. Current methods to measure surface runoff (e.g., natural runoff plots, rainfall simulation and overland flow experiments, modeling approaches) have many advantages but can be prohibitively expensive, may require considerable maintenance, and/or result in significant disturbance during installation. To address these limitations, we assessed a relatively new and underused method for monitoring runoff, the Upwelling Bernoulli Tube (UBeTube). The UBeTube is a low-cost, passive runoff monitoring method that estimates runoff from the height of water flowing out of a slot machined in the side of a vertical tube. In this study, we evaluated the UBeTube across a range of flow rates with three specific objectives: 1) calibrate the UBeTube measurements using clean water, 2) assess the impacts from varying sediment loads on UBeTube measurement accuracy, and 3) evaluate accuracy under conditions similar to those on undisturbed and disturbed rangelands. We found that properly calibrated UBeTubes could be a relatively accurate runoff monitoring method on rangelands (mean percent error = 7.7% clean water calibration, 34.1% sediment loading, 35.2% undisturbed overland flow, 17.7% disturbed overland flow). UBeTubes provide an alternative method to monitor runoff on rangelands that can augment current methods by providing near real-time measurements of runoff generated during natural precipitation events. Easily and rapidly deployed across the landscape, UBeTubes could allow for the relative measurement of spatially variable hydrologic dynamics and serve as another source of information for management decision-making processes and the creation of sustainable strategies for rangeland development.

Recently, hybrid perovskites have gained attention as sensitizers for molecular triplet generation. Layered, two-dimensional (2D) perovskites are especially well-suited for this purpose because the triplet donor (inorganic framework) and triplet acceptor (organic layer) are self-assembled into adjacent sheets, so that with the appropriate energetics, triplets can be driven across the interface. Here we examine interlayer energy transfer in a series of mixed-halide Dion-Jacobson 2D perovskites containing divalent naphthalene cations. We find that the sensitized phosphorescence in these compounds is dominated by naphthalene triplet excimer emission, but when the inorganic exciton is tuned near resonance with the naphthalene triplet, naphthalene monomer phosphorescence competes with triplet excimer formation. The interlayer energy-transfer process is further revealed by ultrafast transient absorption spectroscopy through kinetic variations in triplet excimer formation times. Ultimately, gaining control over interlayer interactions in 2D perovskites through cation design will help uncover new functions and applications for these materials.

Photoanodes containing a WO3/BiVO4 heterojunction have demonstrated promising photoelectrochemical water splitting performance, but the ability to effectively passivate the WO3/BiVO4 interface has limited charge transport and collection. Here, the WO3/BiVO4 interface is passivated with a sulfur-modified Bi2O3 interfacial layer with a staggered band edge alignment to facilitate charge transfer and lifetime. Additionally, BiVO4 was co-doped with Ga3+ at Bi3+ sites and W6+ at V5+ sites (i.e., (Ga,W):BiVO4) to improve the light absorption and photogenerated charge carrier concentration. The optimized WO3/S:Bi2O3/(Ga,W):BiVO4 photoanode exhibited a photocurrent density of 4.0 ± 0.2 mA cm−2 compared to WO3/(Ga,W):BiVO4 with 2.8 ± 0.12 mA cm−2 at 1.23 VRHE in K2HPO4 under simulated AM 1.5G illumination. Time-resolved photoluminescence spectroscopic analysis of the WO3/S:Bi2O3/(Ga,W):BiVO4 electrode validated the enhanced interfacial charge transfer kinetics. In operando femto- and nano-second transient absorption spectroscopy confirmed the presence of long-lived photogenerated charge carriers and revealed lower recombination initially due to rapid charge separation of WO3/S:Bi2O3/(Ga,W):BiVO4. The distribution and role of sulfur was further investigated using EDAX, XPS and TOF-SIMS depth profiling. Finally, a Co-Pi co-catalyst layer was added to achieve a photocurrent of 5.1 ± 0.25 mA cm−2 and corresponding H2 generation rate of 67.3 μmol h−1 cm−2 for the WO3/S:Bi2O3/(Ga,W):BiVO4/Co-Pi photoanode.

Photoinduced electron transfer into mesoporous oxide substrates is well-known to occur efficiently for both singlet and triplet excited states in conventional metal-to-ligand charge transfer (MLCT) dyes. However, in all-organic dyes that have the potential for producing two triplet states from one absorbed photon, called singlet fission dyes, the dynamics of electron injection from singlet vs. triplet excited states has not been elucidated. Using applied bias transient absorption spectroscopy with an anthradithiophene-based chromophore (ADT-COOH) adsorbed to mesoporous indium tin oxide (nanoITO), we modulate the driving force and observe changes in electron injection dynamics. ADT-COOH is known to undergo fast triplet pair formation in solid-state films. We find that the electronic coupling at the interface is roughly one order of magnitude weaker for triplet vs. singlet electron injection, which is potentially related to the highly localized nature of triplets without significant charge-transfer character. Through the use of applied bias on nanoITO:ADT-COOH films, we map the electron injection rate constant dependence on driving force, finding negligible injection from triplets at zero bias due to competing recombination channels. However, at driving forces greater than −0.6 eV, electron injection from the triplet accelerates and clearly produces a trend with increased applied bias that matches predictions from Marcus theory with a metallic acceptor., The rate of photoinduced electron transfer from triplet excited states after singlet fission in molecules adsorbed to mesoporous oxide substrates is shown through transient absorption studies to depend systematically on applied bias.

Singlet fission (SF) has the potential to bypass the Shockley–Queisser limit for solar cell efficiency through the production of two electron–hole pairs per photon. However, in polycrystalline pent...

Summary Simultaneously improving device efficiency and stability is the most important issue in perovskite solar cell (PSC) research. Here, we strategically introduce a multi-functional interface layer (MFIL) with integrated roles of: (1) electron transport, (2) moisture barrier, (3) near-infrared photocurrent enhancement, (4) trap passivation, and (5) ion migration suppression to enhance the device performance. The narrow-band-gap non-fullerene acceptor, Y6, was screened out to replace the most commonly used PCBM in the inverted PSCs. A significantly improved power conversion efficiency of 21.0% was achieved, along with a remarkable stability (up to 1,700 h) without encapsulation under various external stimuli (light, heat, and moisture). Furthermore, systematic studies of the molecular orientation or passivation and the charge carrier dynamics at the interface between perovskite and MFIL were presented. These results offer deep insights for designing advanced interlayers and establish the correlations between molecular orientation, interface molecular bonding, trap state density, non-radiation recombination, and the device performance.

Copper(II) formate is efficiently incorporated into the pores of a 2D imine-based covalent organic framework (COF) via coordination with the phenol and imine groups. The coordinated metal ion is th...

Colloidal quantum dots (QDs) have emerged as versatile and efficient scaffolds to absorb light and then manipulate, direct, and convert that energy into other useful forms of energy. The QD characteristics (optical, electrical, physical) can be readily tuned via solution phase chemistries in order to affect the flow of energy, initially contained in the photons of light, using rational design. Key parameters under control are the size and shape, internal composition (e.g., alloys, core/shell heterostructures, semiconductor/metal interfaces), surface composition (ligand chemistries), and film composition (e.g., QD–QD electronic coupling, bulk heterostructure formation, QD/biological interfaces). In this review, we summarize recent progress using QDs in energy conversion architectures with the express goal of transforming optical energy to other forms of energy, including electricity, photons with different energies, and chemical bonds, i.e., photovoltaics, photon up- or down-conversion, and photocatalytic process, respectively. The advantages of using QDs in absorbing and then directing and converting optical energy over molecular chromophores are highlighted. Finally, we discuss ongoing challenges and opportunities associated with using QDs for absorbing, manipulating and directing the flow of energy.

In singlet fission (SF) the initially formed correlated triplet pair state, 1(TT), may evolve toward independent triplet excitons or higher spin states of the (TT) species. The latter result is often considered undesirable from a light harvesting perspective but may be attractive for quantum information sciences (QIS) applications, as the final exciton pair can be spin-entangled and magnetically active with relatively long room temperature decoherence times. In this study we use ultrafast transient absorption (TA) and time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy to monitor SF and triplet pair evolution in a series of alkyl silyl-functionalized pentadithiophene (PDT) thin films designed with systematically varying pairwise and long-range molecular interactions between PDT chromophores. The lifetime of the (TT) species varies from 40 ns to 1.5 μs, the latter of which is associated with extremely weak intermolecular coupling, sharp optical spectroscopic features, and complex TR-EPR spectra that are composed of a mixture of triplet and quintet-like features. On the other hand, more tightly coupled films produce broader transient optical spectra but simpler TR-EPR spectra consistent with significant population in 5(TT)0. These distinctions are rationalized through the role of exciton diffusion and predictions of TT state mixing with low exchange coupling J versus pure spin substate population with larger J. The connection between population evolution using electronic and spin spectroscopies enables assignments that provide a more detailed picture of triplet pair evolution than previously presented and provides critical guidance for designing molecular QIS systems based on light-induced spin coherence., Pentadithiophene derivatives produce triplet pairs efficiently with secondary spin state evolution that depends on their unique intermolecular juxtapositions.

The photo-driven process of singlet fission generates coupled triplet pairs (TT) with fundamentally intriguing and potentially useful properties. The quintet 5 TT 0 sublevel is particularly interesting for quantum information because it is highly entangled, is addressable with microwave pulses, and could be detected using optical techniques. Previous theoretical work on a model Hamiltonian and nonadiabatic transition theory, called the JDE model, has determined that this sublevel can be selectively populated if certain conditions are met. Among the most challenging, the molecules within the dimer undergoing singlet fission must have their principal magnetic axes parallel to one another and to an applied Zeeman field. Here, we present time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy of a single crystal sample of a tetracenethiophene compound featuring arrays of dimers aligned in this manner, which were mounted so that the orientation of the field relative to the molecular axes could be controlled. The observed spin sublevel populations in the paired TT and unpaired (T+T) triplets are consistent with predictions from the JDE model, including preferential 5 TT 0 formation at z ‖ B 0 , with one caveat—two 5 TT spin sublevels have little to no population. This may be due to crossings between the 5 TT and 3 TT manifolds in the field range investigated by TR-EPR, consistent with the intertriplet exchange energy determined by monitoring photoluminescence at varying magnetic fields.

Changing seasonal precipitation patterns prompted by climate change are likely causing increasing degradation of adobe architecture in the American Southwest. This deterioration includes surface erosion and catastrophic collapse. This study examines the impact of changing rainfall patterns on untreated adobe walls to understand how damage occurs and anticipate future impacts. To complete the study, we constructed 20 adobe test walls. Using a portable rain simulator, each wall was subjected to two rainfall experiments: high-intensity rainfall simulations (rain intensity variable) and low-intensity rainfall simulations (rain event number variable). Wall-degradation metrics (material loss, volume loss, affected surface area, and cavity depth) were calculated for each wall using pre- and post-simulation LiDAR scans. Internal wall moisture was also measured with embedded volumetric water content sensors. In the high-intensity experiment, the lines of best-fit for material loss and affected surface area show that surface erosion increases with rain intensity, while cavity depth remains consistent. Linear models and post-hoc tests indicate material loss and affected surface area is significantly different for each high-intensity rainfall treatment. Furthermore, the interior of each wall remained relatively dry demonstrating that rain intensity is not a strong predictor of interior wall moisture. In the low-intensity rainfall experiment, the rainfall simulations yielded statistically similar erosion and interior wall moisture results. Greater infiltration occurred under low-intensity long-duration rain conditions, while greater surficial damage occurred under high-intensity rain conditions. In conclusion, changing weather regimes are bringing more intense rainfall events to the arid American Southwest. This study suggests that more frequent high intensity rain events will cause increasing damage to adobe walls. Resource managers will need to adapt current management strategies to account for this change.

Molecular spin systems based on photoexcited triplet pairs formed via singlet fission (SF) are attractive as carriers of quantum information because of their potentially pure and controllable spin polarization, but developing systems that offer optical routes to readout as well as initialization is challenging. Herein, we characterize the electron spin magnetic resonance change in the photoluminescence intensity for a tailored organic molecular crystal while sweeping a microwave drive up to 10 GHz in a broadband loop structure. We observe resonant transitions for both triplet and quintet spin sublevel populations showing their optical sensitivity and revealing the zero-field parameters for each. We map the evolution of these spectra in both microwave frequency and magnetic field, producing a pattern of optically detected magnetic resonance (ODMR) peaks. Fits to these data using a suitable model suggest significant spin polarization in this system with orientation selectivity. Unusual excitation intensity dependence is also observed, which inverts the sign of the ODMR signal for the triplet features, but not for the quintet. These observations demonstrate optical detection of the spin sublevel population dictated by SF and intermolecular geometry, and highlight anisotropic and multi-scale dynamics of triplet pairs.

While interlayer triplet energy transfer has been studied in Ruddlesden-Popper 2D perovskites containing monovalent naphthalene cations, the photophysical properties of their Dion-Jacobson analogue have not been reported. Here we examine interlayer energy transfer in a series of mixed-halide Dion-Jacobson 2D perovskites containing divalent naphthalene cations. We find that sensitized phosphorescence in these compounds is dominated by naphthalene triplet excimer emission, but when the lead halide exciton is tuned near resonance with the triplet of naphthalene, emission from the naphthalene triplet monomer competes with triplet excimer formation. Interlayer energy transfer in these compounds is further supported by ultrafast transient absorption spectroscopy.

Singlet fission promises to surpass the Shockley–Queisser limit for single-junction solar cell efficiency through the production of two electron–hole pairs per incident photon. However, this promise has not been fulfilled because singlet fission produces two low-energy triplet excitons that have been unexpectedly difficult to dissociate into free charges. To understand this phenomenon, we study charge separation from triplet excitons in polycrystalline pentacene using an electrochemical series of 12 different guest electron-acceptor molecules with varied reduction potentials. We observe separate optima in the charge yield as a function of driving force for singlet and triplet excitons, including inverted regimes for the dissociation of both states. Molecular acceptors can thus provide a strategic advantage to singlet fission solar cells by suppressing singlet dissociation at optimal driving forces for triplet dissociation. However, even at the optimal driving force, the rate constant for charge transfer from the triplet state is surprisingly small, ~107 s−1, presenting a previously unidentified obstacle to the design of efficient singlet fission solar cells. Singlet fission produces two low-energy triplet excitons that are difficult to dissociate into free charges. Now, separate optima in charge yield have been observed as a function of driving force for singlet and triplet excitons in pentacene. At optimal driving forces, the triplet-exciton dissociation rate is at least five orders of magnitude smaller than the singlet-exciton dissociation rate.

Crystal structures, singlet fission (SF) rate constants, and other photophysical properties are reported for three fluorinated derivatives of 1,3-diphenylisobenzofuran and compared with those of the two crystal forms of the parent. The results place constraints on the notion that the effects of molecular packing on SF rates could be studied separately from effects of chromophore structural changes by examining groups of chromophores related by weakly perturbing substitution if their crystal structures are different. The results further provide experimental evidence that dimer-based models of SF are not sufficiently general and that trimer- and possibly even higher oligomer-based or many-body models need to be formulated.

Singlet fission (SF), the generation of two triplet excitons per the absorption of one photon, is a promising strategy for increasing the efficiency of solar cells beyond the theoretical Shockley–Queisser limit of 34%. Upon photon absorption by a SF molecule, the initially created singlet excited state (S1) interacts with a neighboring chromophore and is first transformed into a triplet pair (TT), which can be subsequently separated into independent triplet excitons (2T1). These independent triplet excitons can be harvested through triplet charge extraction or triplet energy transfer to an acceptor. Research on SF systems has revealed rates and efficiencies of triplet formation and triplet pair decorrelation that are strongly dependent on interchromophore coupling, which is dictated by molecular structure and the resulting geometrical arrangement of chromophores adopted in covalent (e.g., dimers) and noncovalent (e.g., films and crystals) systems. Incorporation of SF materials into realistic device archit...

Shrub encroachment of semiarid grasslands is influenced by connected runoff and erosion patterns that preferentially accumulate resources under vegetated patches (canopy microsites) and deplete interspaces. Soil loss from dryland hillslopes results when areas of bare ground become structurally and functionally connected through overland flow. Although these patterns have been well-described, uncertainty remains regarding how these feedbacks respond to restoration practices. This study compared the structure and hydrologic function of a shrub-encroached semiarid grassland treated five years prior with the herbicide, tebuthiuron, to that of an adjacent untreated grassland. Through a series of hydrologic experiments conducted at increasing spatial scales, vegetation and soil structural patterns were related to runoff and erosion responses. At a fine scale (0.5 m2), rainfall simulations (120 mm·h-1 rainfall intensity; 45 min) showed herbicided shrub canopy microsites had greater infiltration capacities (105 and 71 mm·h-1 terminal infiltration rates) and were less susceptible to splash-sheet erosion (3 and 26 g sediment yield) than untreated shrub canopy microsites, while interspaces were statistically comparable between study sites. Concentrated flow simulations at a coarse scale (~9 m2) revealed that gaps between the bases of vegetation (i.e. basal gaps) > 2 mwere positively related to both concentrated flow runoff (r = 0.72, p = 0.008) and sediment yield (r = 0.70, p = 0.012). Modeled hillslope-scale (50 m2) runoff and erosion (120 mm·h-1 rainfall intensity; 45 min) indicated less soil loss in the tebuthiuron-treated site (1.78 Mg·ha-1 tebuthiuron; 3.19 Mg·ha-1 untreated), even though runoff was similar between sites. Our results suggest interspaces in shrub-encroached grasslands continue to be runoff sources following herbicide-induced shrub mortality and may be indicators of runoff responses at larger spatial scales. In contrast, sediment sources are limited post-treatment due to lesser sediment detachment from sheet-splash and concentrated flow processes. Reduced sediment supplies provide evidence that connectivity feedbacks that sustain a shrub-dominant ecological state may have been dampened post-treatment. Our study also highlights the utility of simple measures of structural connectivity, such as basal gaps, as an indicator of hillslope susceptibility to increased runoff and erosion.

Pinyon (Pinus spp.) and juniper (Juniperus spp.) woodland encroachment into sagebrush (Artemisia spp.) steppe communities throughout western North America has substantially altered the vegetation structure and hydrologic function of one of the most ecologically important rangeland ecosystems in the world. Various pinyon and juniper tree removal practices are employed to re-establish sagebrush steppe vegetation and an associated resource-conserving ecohydrologic function. The effectiveness of these practices is highly variable owing to the vast domain in which woodland encroachment occurs, climate fluctuations, differences in treatment applications, and myriads of pre-treatment conditions and post-treatment land uses. This study evaluated the long-term (13 years post-treatment) effectiveness of prescribed fire and mechanical tree removal to re-establish sagebrush steppe vegetation and associated spatial patterns in ground surface conditions and soil hydrologic properties of two woodland-encroached sites. Specifically, we assessed the effects of tree removal on: (1) vegetation and ground cover at the hillslope scale (990 m2 plots) and (2) associated spatial patterns in point-scale ground surface conditions and soil hydrologic properties along transects extending from tree bases and into the intercanopy areas between trees. Both sites were in mid to late stages of woodland encroachment with extensive bare conditions (~60&ndash, 80% bare ground) throughout a degraded intercanopy area (~75% of the domain) surrounding tree islands (~25% of domain, subcanopy areas). All treatments effectively removed mature tree cover and increased hillslope vegetation. Enhanced herbaceous cover (4&ndash, 15-fold increases) in burned areas reduced bare interspace (bare area between plants) by at least 4-fold and improved intercanopy hydraulic conductivity (&gt, than 2-fold) and overall ecohydrologic function. Mechanical treatments retained or increased sagebrush and generally increased the intercanopy herbaceous vegetation. Intercanopy ground surface conditions and soil hydrologic properties in mechanical treatments were generally similar to those in burned areas but were also statistically similar to the same measures in untreated areas in most cases. This suggests that vegetation and ground surface conditions in mechanical treatments are trending toward a significantly improved hydrologic function over time. Treatments had limited impact on soil hydrologic properties within subcanopy areas, however, burning did reduce the soil water repellency strength and the occurrence of strong soil water repellency underneath trees by three- to four-fold. Overall, the treatments over a 13-year period enhanced the vegetation, ground surface conditions, and soil hydrologic properties that promote infiltration and limit runoff generation for intercanopy areas representing ~75% of the area at the sites. However, ecological tradeoffs in treatment alternatives were evident. The variations in woodland responses across sites, treatments, and measurement scales in this long-term study illustrate the complexity in predicting vegetation and hydrologic responses to tree removal on woodland-encroached sagebrush sites and underpin the need and value of multi-scale long-term studies.

Mitigating and reversing negative ecohydrologic impacts of woody plant encroachment is of global concern. Current knowledge on the ramifications of woody plant encroachment and landscape responses to management is largely based on short-term or point-in-time field studies. The limited longevity of these studies is often dictated by the short-term nature of funding sources and associated infrastructure. Short-term studies advance process-based ecohydrologic knowledge of natural systems and yield valuable insight on treatment effects for various practices to mitigate woody plant encroachment. However, scientists, public and private land owners, and policy makers require knowledge of long-term effectiveness of treatment practices and associated conceptual and quantitative tools to successfully target land management expenditures and actions. This presentation highlights science-based knowledge and ecohydrologic model advancements in management of woody plant encroachment over a nearly 15 yr study period associated with ecohydrologic research at multiple sites in the sagebrush biome within the Great Basin Region of the western United States (the SageSTEP study, www.sagestep.org). The sagebrush biome is considered one of the most ecologically important and imperiled rangeland domains in the United States. A primary driver of degradation to the sagebrush biome is encroachment by pinyon and juniper conifers. These encroaching trees can outcompete sagebrush vegetation for soil and water resources and ultimately propagate and perpetuate pinyon and juniper woodland conditions with extensive bare ground and amplified runoff and soil loss. This study evaluated the ecohydrologic impacts of pinyon and juniper encroachment on sagebrush steppe and the long-term effectiveness of various tree-removal practices to restore sagebrush steppe vegetation and associated ecohydrologic function. Experiments in the study include assessment of vegetation, ground cover, soils, and infiltration, runoff, and erosion processes spanning point to hillslope spatial scales prior to tree removal treatments and at time periods 1 yr, 2 yr, 9 yr, and 13 yr after tree removal. Research products include: 1) advances in conceptual and quantitative understanding of linkages in vegetation and hydrology and erosion processes for the sagebrush steppe ecosystem, 2) enhancements to various conceptual ecological models and the Rangeland Hydrology and Erosion Model (RHEM) tool, 3) advanced understanding of the effectiveness of various tree-removal practices across diverse conditions in the sagebrush biome, and 4) delivery of an extensive publicly-available dataset for developing, enhancing, and/or evaluating other conceptual and quantitative ecohydrologic and erosion models. Lastly, the collective advances in science-based knowledge and modeling tools from the study demonstrate the utility and value of funding and conducting long-term ecohydrological research, particularly for ecologically important biomes around the world.

Hybrid organic-inorganic halide perovskites have been proposed in many optoelectronic applications, but critical to their increasing functionality and utility is understanding and controlling carrier transport. Here, we use light-induced transient grating spectroscopy to probe directly carrier transport in polycrystalline methylammonium lead iodide perovskite thin films using a weakly perturbative and noncontact method. The data reveal intrinsic diffusion characteristics of the charge carriers in the material and agree well with a simulated model of charge transport in which grain boundaries act as barriers to carrier movement.

The hollow cores and well-defined diameters of single-walled carbon nanotubes (SWCNTs) allow for creation of one-dimensional hybrid structures by encapsulation of various molecules. Absorption and near-infrared photoluminescence-excitation (PLE) spectroscopy reveal that the absorption spectrum of encapsulated 1,3-bis[4-(dimethylamino)phenyl]-squaraine dye molecules inside SWCNTs is modulated by the SWCNT diameter, as observed through excitation energy transfer (EET) from the encapsulated molecules to the SWCNTs, implying a strongly diameter dependent stacking of the molecules inside the SWCNTs. Transient absorption spectroscopy, simultaneously probing the encapsulated dyes and the host SWCNTs, demonstrates this EET, which can be used as a route to diameter-dependent photosensitization, to be fast (sub-picosecond). A wide series of SWCNT samples is systematically characterized by absorption, PLE, and resonant Raman scattering (RRS), also identifying the critical diameter for squaraine filling. In addition, we find that SWCNT filling does not limit the selectivity of subsequent separation protocols (including polyfluorene polymers for isolating only semiconducting SWCNTs and aqueous two-phase separation for enrichment of specific SWCNT chiralities). The design of these functional hybrid systems, with tunable dye absorption, fast and efficient EET, and the ability to remove all metallic SWCNTs by subsequent separation, demonstrates potential for implementation in photoconversion devices.

A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer–Emmet–Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ∼37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (∼1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features in FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.

Electron injection competes with singlet fission in disordered monolayers of tetracene and pentacene-based dyes on mesoporous TiO2 photoelectrodes., We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition of an alumina layer slows down electron injection, allowing the formation of triplets from singlet fission in 40 ps. However, the triplets do not inject electrons, which is likely due to a lack of sufficient driving force for triplet dissociation. These results point to the critical balance required between efficient singlet fission and appropriate energetics for interfacial charge transfer.

The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. We investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side-chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these "singlet fission polymers" to produce the long-lived triplets needed to realize efficient photovoltaic devices.

Rainfall simulation and overland-flow experiments enhance understanding of surface hydrology and erosion processes, quantify runoff and erosion rates, and provide valuable data for developing and testing predictive models. We present a unique dataset (1021 experimental plots) of rainfall simulation (1300 plot runs) and overland flow (838 plot runs) experimental plot data paired with measures of vegetation, ground cover, and surface soil physical properties spanning point to hillslope scales. The experimental data were collected at three sloping sagebrush (Artemisia spp.) sites in the Great Basin, USA, each subjected to woodland-encroachment and with conditions representative of intact wooded-shrublands and 1–9 yr following wildfire, prescribed fire, and/or tree cutting and shredding tree-removal treatments. The methodologies applied in data collection and the cross-scale experimental design uniquely provide scale-dependent, separate measures of interrill (rainsplash and sheetflow processes) and concentrated overland-flow runoff and erosion rates along with collective rates for these same processes combined over the patch scale (tens of meters). The dataset provides a valuable source for developing, assessing, and calibrating/validating runoff and erosion models applicable to diverse plant community dynamics with varying vegetation, ground cover, and surface soil conditions. The experimental data advance understanding and quantification of surface hydrologic and erosion processes for the research domain and potentially for other patchy-vegetated rangeland landscapes elsewhere. Lastly, the unique nature of repeated measures spanning numerous treatments and time scales delivers a valuable dataset for examining long-term landscape vegetation, soil, hydrology, and erosion responses to various management actions, land use, and natural disturbances. The dataset is available from the National Agricultural Library at https://data.nal.usda.gov/search/type/dataset (DOI: https://doi.org/10.15482/USDA.ADC/1504518; Pierson et al., 2019).

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model. Published under license by AIP Publishing.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) are attractive light-harvesting components for solar photoconversion schemes and architectures, and selective polymer extraction has emerged as a powerful route to obtain highly pure s-SWCNT samples for electronic applications. Here we demonstrate a novel method for producing electronically coupled thin films of near-monochiral s-SWCNTs without wrapping polymer. Detailed steady-state and transient optical studies on such samples provide new insights into the role of the wrapping polymer on controlling intra-bundle nanotube–nanotube interactions and exciton energy transfer within and between bundles. Complete removal of polymer from the networks results in rapid exciton trapping within nanotube bundles, limiting long-range exciton transport. The results suggest that intertube electronic coupling and associated exciton delocalization across multiple tubes can limit diffusive exciton transport. The complex relationship observed here between exciton delocalization, trapping, and long-range transport, helps to inform the design, preparation, and implementation of carbon nanotube networks as active elements for optical and electronic applications.

The marriage of colloidal semiconductor nanocrystals and functional organic molecules has brought unique opportunities in emerging photonic and optoelectronic applications. Traditional semiconductor nanocrystals have been widely demonstrated to initiate efficient triplet energy transfer at the nanocrystal–acene interface. Herein, we report that unlike conventional semiconductor nanocrystals, lead halide perovskite nanocrystals promote an efficient Dexter-like singlet energy transfer to surface-anchored pentacene molecules rather than triplet energy transfer. Subsequently, molecular pentacene triplets are efficiently generated via singlet fission on the nanocrystal surface. Our demonstrated strategy not only unveils the obscure energy dynamics between perovskite nanocrystal and acenes, but also brings important perspectives of utilizing singlet fission throughout the solar spectrum.

A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied. The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.

A strong interaction of a semiconductor with a below-bandgap laser pulse causes a blue-shift of the bandgap transition energy, known as the optical Stark effect. The energy shift persists only during the pulse duration with an instantaneous response time. The optical Stark effect has practical relevance for applications, including quantum information processing and communication, and passively mode-locked femtosecond lasers. Here we demonstrate that solution-processable lead-halide perovskites exhibit a large optical Stark effect that is easily resolved at room temperature resulting from the sharp excitonic feature near the bandedge. We also demonstrate that a polarized pump pulse selectively shifts one spin state producing a spin splitting of the degenerate excitonic states. Such selective spin manipulation is an important prerequisite for spintronic applications. Our result implies that such hybrid semiconductors may have great potential for optoelectronic applications beyond photovoltaics., The band gap of bulk semiconductors widens when excited by sub-bandgap wavelengths at low temperature—it's the optical Stark effect. Here, the authors measure a room temperature optical Stark effect in lead halide perovskite films, due to their well-resolved excitonic transitions.

By direct imaging of singlet and triplet populations with ultrafast microscopy, it is shown that the triplet diffusion length and singlet fission yield can be simultaneously optimized for tetracene and its derivatives, making them ideal structures for application in bilayer solar cells.

Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films. We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.

Two isomers of both the lowest excited singlet (S1) and triplet (T1) states of the directly para, para'-connected covalent dimer of the singlet-fission chromophore 1,3-diphenylisobenzofuran have been observed. In one isomer, excitation is delocalized over both halves of the dimer, and in the other, it is localized on one or the other half. For a covalent dimer in solution, such "excitation isomerism" is extremely rare. The vibrationally relaxed isomers do not interconvert, and their photophysical properties, including singlet fission, differ significantly.

The efficiency of thin-film organic photovoltaic (OPV) devices relies heavily upon the transport of excitons to type-II heterojunction interfaces, where there is sufficient driving force for exciton dissociation and ultimately the formation of charge carriers. Semiconducting single-walled carbon nanotubes (SWCNTs) are strong near-infrared absorbers that form type-II heterojunctions with fullerenes such as C60. Although the efficiencies of SWCNT-fullerene OPV devices have climbed over the past few years, questions remain regarding the fundamental factors that currently limit their performance. In this study, we determine the exciton diffusion length in the C60 layer of SWCNT-C60 bilayer active layers using femtosecond transient absorption measurements. We demonstrate that hole transfer from photoexcited C60 molecules to SWCNTs can be tracked by the growth of narrow spectroscopic signatures of holes in the SWCNT "reporter layer". In bilayers with thick C60 layers, the SWCNT charge-related signatures display a slow rise over hundreds of picoseconds, reflecting exciton diffusion through the C60 layer to the interface. A model based on exciton diffusion with a Beer-Lambert excitation profile, as well as Monte Carlo simulations, gives the best fit to the data as a function of C60 layer thickness using an exciton diffusion length of approximately 5 nm.

We report third-order nonlinear coefficient values and decay time kinetics vs. halide composition (CH3NH3PbBr3 and CH3NH3PbBr2I), temperature, and excitation wavelength. The maximum values of the third-order nonlinear susceptibility χ(3) (∼1.6 × 10−6 esu) are similar to or larger than many common third-order materials. The source of the nonlinearity is shown to be primarily excitonic in the tribromide film by virtue of its strong enhancement near the exciton resonance. Nonresonant excitation reduces the nonlinearity significantly, as does increasing the temperature. Substitution of one I for one Br also reduces the nonlinearity by at least one order of magnitude, presumably due to the lack of strong exciton resonance in the substituted form. The thin films are stable, highly homogenous (lacking significant light scattering), and simple and inexpensive to fabricate, making them potentially useful in a variety of optoelectronic applications in which wavelength selectivity is important.