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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 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

On hydromagnetic wave interactions in collisionless, high- β plasmas

We describe the interaction of parallel-propagating Alfvén waves with ion-acoustic waves and other Alfvén waves, in magnetized, high- β collisionless plasmas. This is accomplished through a combination of analytical theory and numerical fluid simulations of the Chew–Goldberger–Low (CGL) magnetohydrodynamic (MHD) equations closed by Landau-fluid heat fluxes. An asymptotic ordering is employed to simplify the CGL-MHD equations and derive solutions for the deformation of an Alfvén wave that results from its interaction with the pressure anisotropy generated either by an ion-acoustic wave or another, larger-amplitude Alfvén wave. The difference in time scales of acoustic and Alfvénic fluctuations at high- β means that interactions that are local in wavenumber space yield little modification to either mode within the time it takes the acoustic wave to Landau damp away. Instead, order-unity changes in the amplitude of Alfvénic fluctuations can result after interacting with frequency-matched acoustic waves. Additionally, we show that the propagation speed of an Alfvén-wave packet in an otherwise homogeneous background is a function of its self-generated pressure anisotropy. This allows for the eventual interaction of separate co-propagating Alfvén-wave packets of differing amplitudes. The results of the CGL-MHD simulations agree well with these predictions, suggesting that theoretical models relying on the interaction of these modes should be reconsidered in certain astrophysical environments. Applications of these results to weak Alfvénic turbulence and to the interaction between the compressive and Alfvénic cascades in strong, collisionless turbulence are also discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Role of ion acoustic instability in magnetic reconnection

We report on a first-principles numerical study of magnetic reconnection in plasmas with different initial ion-to-electron temperature ratios. In cases where this ratio is significantly below unity, we observe intense wave activity in the diffusion region, driven by the ion-acoustic instability. Our analysis shows that the dominant macroscopic effect of this instability is to drive substantial ion heating. In contrast to earlier studies reporting significant anomalous resistivity, we find that anomalous contributions due to the ion-acoustic instability are minimal. These results shed light on the dynamical impact of this instability on reconnection processes, offering new insights into the fundamental physics governing collisionless reconnection.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

Probing Surface Defects of InP Quantum Dots Using Phosphorus Kα and Kβ X-ray Emission Spectroscopy

Synthetic efforts to prepare indium phosphide (InP) quantum dots (QDs) have historically generated emissive materials with lower than unity quantum yields. This property has been attributed to structural and electronic defects associated with the InP core as well as the chemistry of the shell materials used to overcoat and passivate the InP surface. Consequently, the uniformity of the core–shell interface plays a critical role. Using X-ray emission spectroscopy (XES) performed with a recently developed benchtop spectrometer, we studied the evolution of oxidized phosphorus species arising across a series of common, but chemically distinct, synthetic methods for InP QD particle growth and subsequent ZnE (E = S or Se) shell deposition. XES afforded us the ability to measure the speciation of phosphorus reliably, quantitatively, and more efficiently (with respect to both the quantity of material required and the speed of the measurement) than with traditional techniques, i.e., X-ray photoelectron spectroscopy and magic angle spinning solid state nuclear magnetic resonance spectroscopy. In conclusion, our findings indicate that even with deliberate care to prevent phosphorus oxidation during InP core synthesis, typical shelling approaches unintentionally introduce oxidative defects at the core–shell interface, limiting the attainable photoluminescence quantum yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Single-Molecule Fluorescence Spectroscopy of Photosynthetic Systems

Photosynthesis begins when a network of pigment–protein complexes captures solar energy and transports it to the reaction center, where charge separation occurs. When necessary (under low light conditions), photosynthetic organisms perform this energy transport and charge separation with near unity quantum efficiency. Remarkably, this high efficiency is maintained under physiological conditions, which include thermal fluctuations of the pigment–protein complexes and changing local environments. These conditions introduce multiple types of heterogeneity in the pigment–protein complexes, including structural heterogeneity, energetic heterogeneity, and functional heterogeneity. Understanding how photosynthetic light-harvesting functions in the face of these fluctuations requires understanding this heterogeneity, which, in turn, requires characterization of individual pigment–protein complexes. Single-molecule spectroscopy has the power to probe individual complexes. In this review, we present an overview of the common techniques for single-molecule fluorescence spectroscopy applied to photosynthetic systems and describe selected experiments on these systems. We discuss how these experiments provide a new understanding of the impact of heterogeneity on light harvesting and thus how these systems are optimized to capture sunlight under physiological conditions.

14 SOLAR ENERGY↗
DOE OSTI2018

Normalized Quantitative PCR Measurements as Predictors for Ethene Formation at Sites Impacted with Chlorinated Ethenes

Quantitative PCR (qPCR) targeting Dehalococcoides mccartyi (Dhc) biomarker genes supports effective management at sites impacted with chlorinated ethenes. To establish correlations between Dhc biomarker gene abundances and ethene formation (i.e., detoxification), 859 groundwater samples representing 62 sites undergoing monitored natural attenuation or enhanced remediation were analyzed. Dhc 16S rRNA genes and the vinyl chloride (VC) reductive dehalogenase genes bvcA and vcrA were detected in 88% and 61% of samples, respectively, from wells with ethene. Dhc 16S rRNA, bvcA , vcrA , and tceA (implicated in cometabolic reductive VC dechlorination) gene abundances all positively correlated with ethene formation. Significantly greater ethene concentrations were observed when Dhc 16S rRNA gene and VC RDase gene abundances exceeded 10 7 and 10 6 copies L –1 , respectively, and when Dhc 16S rRNA- and bvcA + vcrA -to-total bacterial 16S rRNA gene ratios exceeded 0.1%. Dhc 16S rRNA gene-to- vcrA/bvcA ratios near unity also indicated elevated ethene; yet, no increased ethene was observed in 19 wells where vcrA and/or bvcA gene copy numbers exceeded Dhc cell numbers 10- to 10 000-fold. Approximately one-third of samples with detectable ethene lacked bvcA , vcrA , and tceA , implying that comprehensive understanding of VC detoxification biomarkers has not been achieved. Although the current biomarker suite is incomplete, the data analysis corroborates the value of the available Dhc DNA biomarkers for prognostic and diagnostic groundwater monitoring at sites impacted with chlorinated ethenes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Deciphering Distinct Overpotential-Dependent Pathways for Electrochemical CO 2 Reduction Catalyzed by an Iron–Terpyridine Complex

[Fe(tpyPY2Me)] 2+ ([Fe] 2+ ) is a homogeneous electrocatalyst for converting CO 2 into CO featuring low overpotentials of <100 mV, near-unity selectivity, and high activity with turnover frequencies faster than 100 000 s -1 . To identify the origins of its exceptional performance and inform future catalyst design, we report a combined computational and experimental study that establishes two distinct mechanistic pathways for electrochemical CO 2 reduction catalyzed by [Fe] 2+ as a function of applied overpotential. Electrochemical data shows the formation of two catalytic regimes at low (η TOF/2 of 160 mV) and high (η TOF/2 of 590 mV) overpotential plateaus. We propose that at low overpotentials [Fe] 2+ undergoes a two-electron reduction, two-proton-transfer mechanism (electrochemical-electrochemical-chemical-chemical, EECC), where turnover occurs through the dicationic iron complex, [Fe] 2+ . Computational analysis supports the importance of the singlet ground-state electronic structure for CO 2 binding and that the rate-limiting step is the second protonation in this low-overpotential regime. When more negative potentials are applied, an additional electron-transfer event occurs through either a stepwise or proton-coupled electron-transfer (PCET) pathway, enabling catalytic turnover from the monocationic iron complex ([Fe] + ) via an electrochemical-chemical-electrochemical-chemical (ECEC) mechanism. Comparison of experimental kinetic data obtained from variable controlled potential electrolysis (CPE) experiments with direct product detection with calculated rates obtained from the energetic span model supports the PCET pathway as the most likely mechanism. Moreover, we build upon this mechanistic understanding to propose the design of an improved ligand framework that is predicted to stabilize the key transition states identified in our study and explore their electronic structures using an energy decomposition analysis. Finally, taken together, this work highlights the value of synergistic computational/experimental approaches to decipher mechanisms of new electrocatalysts and direct the rational design of improved platforms.

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

Infrared Fingerprint and Unimolecular Decay Dynamics of the Hydroperoxyalkyl Intermediate (•QOOH) in Cyclopentane Oxidation

A transient carbon-centered hydroperoxyalkyl intermediate (•QOOH) in the oxidation of cyclopentane is identified by IR action spectroscopy with time-resolved unimolecular decay to hydroxyl (OH) radical products that are detected by UV laser-induced fluorescence. Two nearly degenerate •QOOH isomers, β- and γ-QOOH, are generated by H atom abstraction of the cyclopentyl hydroperoxide precursor. Fundamental and first overtone OH stretch transitions and combination bands of •QOOH are observed and compared with anharmonic frequencies computed by second-order vibrational perturbation theory. An OH stretch transition is also observed for a conformer arising from torsion about a low-energy CCOO barrier. Definitive identification of the β-QOOH isomer relies on its significantly lower transition state (TS) barrier to OH products, which results in rapid unimolecular decay and near unity branching to OH products. A benchmarking approach is utilized to compute high-accuracy stationary point energies, most importantly TS barriers, for cyclopentane oxidation (C 5 H 9 O 2 ), building on higher level reference calculations for ethane oxidation (C 2 H 5 O 2 ). The experimental OH product appearance rates are compared with computed statistical microcanonical rates using RRKM theory, including heavy-atom tunneling, thereby validating the computed TS barrier. The results are extended to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclopentane combustion via master-equation modeling. Furthermore, the various torsional and ring puckering states of the wells and transition states are explicitly considered in these calculations.

Chemical calculations↗
DOE OSTI2020

Ultrafast Relaxations in Ruthenium Polypyridyl Chromophores Determined by Stochastic Kinetics Simulations

Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. This treatment assumes that dynamic events are well separated in time, and that the resulting exponential prefactors and phenomenological lifetimes are related directly to primary physical values. Such assumptions break down for coincident absorption, emission, and excited state relaxation that occur in transient absorption and photoluminescence of tris(2,2'-bipyridine)ruthenium(2+) derivatives, confounding the physical meaning of the reported lifetimes. Here, we use inductive modeling and stochastic chemical kinetics to develop a detailed description of the primary ultrafast photophysics in transient spectroscopies of a series of Ru dyes, as an alternative to sums of exponential analysis. Commonly invoked three-level schemes involving absorption, intersystem crossing (ISC), and slow nonradiative relaxation and incoherent emission to the ground state cannot reproduce the experimentally measured spectra. The kinetics simulations reveal that ultrafast decay from the singlet excited state manifold to the ground state competes with ISC to the triplet excited state, whose efficiency was determined to be less than unity. The populations predicted by the simulations are used to estimate the magnitudes of transition dipoles for excited state excitations and evaluate the influence of specific ligands. The mechanistic framework and methodology presented here are entirely general, applicable to other dye classes, and can be extended to include charge injection by molecules bound to semiconductor surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing the Solvation Shells of Lithium Ions in Glyme-Based Electrolytes

Glymes have been extensively studied as solvents for Li-battery electrolytes, most recently in equimolar mixtures with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), due to their ability to form stable solvates. However, directly quantifying free and coordinated glyme molecules in the liquid state has been challenging due to several experimental limitations. Here, in this work, new vibrational probes are demonstrated for studying the solvation structures of diglyme and triglyme in LiTFSI electrolytes. These IR probes make use of an amine group to report the solvation state of glymes at salt-to-solvent molar ratios ranging from 1:5 to 1:10. Characterization of the thermodynamic properties of the solvent exchange occurring in the first solvation shell of lithium ions (Li + ) showed an equilibrium constant for these probes close to unity at room temperature. This result demonstrates that the probes exhibit a similar solvation behavior to their glyme analogue. Concentration dependence studies also revealed a lack of significant amounts of contact ion pairs at the studied concentrations. Moreover, the first solvation shell of Li + appears to be formed by two partially chelating glyme molecules, establishing that even triglyme with multiple chelation sites does not fully coordinate the cation. Complementary molecular dynamics (MD) simulations agree with the experimental results and suggest that at these concentrations, TFSI – predominantly forms solvent-separated ion pairs. However, the simulations do not properly capture the partial solvation structure of the glyme molecules in the solvation shell of Li + as derived from the experiments.

electrolytes↗
DOE OSTI2016

Role of Macromolecular Structure in the Ultrafast Energy and Electron Transfer Dynamics of a Light-Harvesting Polymer

Ultrafast energy and electron transfer (EnT and ET, respectively) are characterized in a light-harvesting assembly based on a π-conjugated polymer (poly(fluorene)) functionalized with broadly absorbing pendant organic isoindigo (iI) chromophores using a combination of femtosecond transient absorption spectroscopy and large-scale computer simulation. Photoexcitation of the π-conjugated polymer leads to near-unity quenching of the excitation through a combination of EnT and ET to the iI pendants. The excited pendants formed by EnT rapidly relax within 30 ps, whereas recombination of the charge-separated state formed following ET occurs within 1200 ps. A computer model of the excited-state processes is developed by combining all-atom molecular dynamics simulations, which provides a molecular-level view of the assembly structure, with a kinetic model that accounts for the multiple excited-state quenching pathways. In conclusion, direct comparison of the simulations with experimental data reveals that the underlying structure has a dramatic effect on the partitioning between EnT and ET in the polymer assembly, where the distance and orientation of the pendants in relation to the backbone serve to direct the dominant quenching pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Cobalt Intercalated Layered NiFe Double Hydroxides for the Oxygen Evolution Reaction

We present a combined experimental and theoretical study to demonstrate that the electrocatalytic activity of NiFe layered double hydroxides (NiFe LDHs) for the oxygen evolution reaction (OER) can be significantly enhanced by systematic cobalt incorporation using coprecipitation and/or intercalation. Electrochemical measurements show that cobalt modified NiFe LDH possesses an enhanced activity for the OER relative to pristine NiFe LDH. The Co-modified NiFe LDH exhibits overpotentials in the range of 290–322 mV (at 10 mA cm –2 ), depending on the degree of cobalt content. Here, the best catalyst, cobalt intercalated NiFe LDH achieved a current density of 10 mA cm –2 at an overpotential of ~265 mV (compared to 310 mV for NiFe LDH), with a near unity (99%) faradaic efficiency and long-term stability. Density functional theory calculations revealed that enhanced activity of Co-modified NiFe LDH could be attributed to the ability of Co to tune the electronic structure of the NiFe LDH so that optimal binding of OER reaction intermediates could be achieved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effect of Block Length and Side Chain Length Ratios on Determining a Multicompartment Micelle Structure

Previous work has identified the importance of the lipophilic-fluorophilic block length ratio R l in predicting the morphology of linear lipophilic-hydrophilic-fluorophilic (hereafter referred to as BAC) micelle systems. Here, a generalized form R of this structural parameter is developed that makes no assumption of BAC triblock copolymer linearity, while still providing accurate predictions of micelle morphology. Here, the morphologies of BAC micelles formed by triblock copolymers with R <<1 or R >>1 have similar features, with the only notable difference being an inversion of the lipophilic and fluorophilic regions. A destabilization of the single-core micelle structure occurs as R approaches unity from either direction. Finally, the extent to which micelle morphology depends on polymer architecture instead of composition alone is examined, with decreased patchiness observed in BAC systems with very long block lengths. Through modification of both the R-value and the polymer architecture, the micelle morphology can be effectively tuned for use in immobilized catalysis and nanoreactor applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Comparison of the Energy-Transfer Rates in Structural and Spectral Variants of the B800–850 Complex from Purple Bacteria

Photosynthetic light harvesting can occur with a remarkable near-unity quantum efficiency. The B800–850 complex, also known as light-harvesting complex 2 (LH2), is the primary light-harvesting complex in purple bacteria and has been extensively studied as a model system. The bacteriochlorophylls of the B800–850 complex are organized into two concentric rings, known as the B800 and B850 rings. However, depending on the species and growth conditions, the number of constituent subunits, the pigment geometry, and the absorption energies vary. While the dynamics of some B800–850 variants have been exhaustively characterized, others have not been measured. Furthermore, a direct and simultaneous comparison of how both structural and spectral differences between variants affect these dynamics has not been performed. In this work, we utilize ultrafast transient absorption measurements to compare the B800 to B850 energy-transfer rates in the B800–850 complex as a function of the number of subunits, geometry, and absorption energies. The nonameric B800–850 complex from Rhodobacter (Rb.) sphaeroides is 40% faster than the octameric B800–850 complex from Rhodospirillum (Rs.) molischianum, consistent with structure-based predictions. In contrast, the blue-shifted B800–820 complex from Rs. molischianum is only 20% faster than the B800–850 complex from Rs. molischianum despite an increase in the spectral overlap between the rings that would be expected to produce a larger increase in the energy-transfer rate. These measurements support current models that contain dark, higher-lying excitonic states to bridge the energy gap between rings, thereby maintaining similar energy-transfer dynamics. Altogether, these results demonstrate that energy-transfer dynamics in the B800–850 complex are robust to the spectral and structural variations between species used to optimize energy capture and flow in purple bacteria.

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

Ultrafast Spin Crossover in a Room-Temperature Ferrimagnet: Element-Specific Spin Dynamics in Photoexcited Cobalt Ferrite

Transition metal complexes capable of photoinduced spin crossover have been greatly investigated because of their potential to enable ultrafast optical control of information processing. Yet, any real application of photoswitchable molecules requires that spin crossover be paired with additional functionality such as long-range magnetic order. Important advances combining these functions are notably reported for a number of bimetallic Prussian Blue analogues; however, to date, PBA-based magnetic photoswitches can only operate below 150 K due to loss of magnetic order. In contrast, cobalt ferrite is a ferrimagnetic semiconductor with a Curie temperature of 790 K and extremely favorable magnetic properties by comparison to state-of-the-art PBAs. The mixed valence electronic structure of cobalt ferrite is reminiscent of cobalt–iron PBA, which is a well-known photoswitch. To investigate the potential for photoswitching in this material, we employ transient XUV spectroscopy to probe charge and spin dynamics with element-specific resolution on the femtosecond time scale. Results show that 400 nm light excites a metal-to-metal charge transfer transition, which drives the crossover of high-spin Co 2+ to low-spin Co 3+ with a time constant of 405 ± 29 fs and an internal quantum efficiency of unity. This result establishes the existence of efficient photoswitching in a new class of robust ferrimagnetic spinel ferrites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Surface Basic Site Effect on Boron-Promoted Platinum Catalysts for Dry Reforming of Methane

Platinum has been shown to be an active catalyst for the dry reforming of methane (DRM), which converts CO 2 and CH 4 into 2CO and 2H 2 (synthesis gases) that can further be processed to produce valuable chemical feedstocks. Catalytic activity is often improved by the addition of promoter atoms, which are typically transition metals or noble metals, such as PtNi and PtSn. Recently, boron has shown to be an effective and low-cost catalyst promoter. Pt/B/SiO 2 catalysts were prepared for DRM catalysis and compared with Pt/SiO 2 catalysts without boron promotion. Both catalysts had similar surface concentrations of platinum, but the catalytic activity at 750 °C after 14 h for boron-containing catalyst was very high, resulting in nearly 100% CO 2 conversion and a H 2 /CO ratio close to unity, compared to 12% CO 2 conversion and H 2 /CO of 0.35 for boron-free Pt/SiO 2 . The catalysts were investigated with X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and CO 2 temperature-programmed desorption (CO 2 -TPD) to identify the deactivating factors. It was determined that neither platinum nanoparticle sintering nor coking was a significant factor in catalyst deactivation; instead, boron had an effect on the reactive surface groups on the SiO 2 support. Finally, these surface groups, such as hydroxyls and surface basic sites, enhance the adsorption of CO 2 and potentially stabilize intermediate carbonate species, resulting in a high CO 2 conversion for boron-promoted platinum catalysts.

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

Spin Uncoupling in Chemisorbed OCCO and CO 2 : Two High-Energy Intermediates in Catalytic CO 2 Reduction

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an average gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2 , conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.

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

Mercury Chalcogenide Nanoplatelet–Quantum Dot Heterostructures as a New Class of Continuously Tunable Bright Shortwave Infrared Emitters

Despite broad applications in imaging, energy conversion, and telecommunications, few nanoscale moieties emit light efficiently in the shortwave infrared (SWIR, 1000–2000 nm or 1.24–0.62 eV). We report quantum-confined mercury chalcogenide (HgX, where X = Se or Te) nanoplatelets (NPLs) can be induced to emit bright (QY > 30%) and tunable (900–1500+ nm) infrared emission from attached quantum dot (QD) “defect” states. Here, we demonstrate near unity energy transfer from NPL to these QDs, which completely quench NPL emission and emit with a high QY through the SWIR. This QD defect emission is kinetically tunable, enabling controlled midgap emission from NPLs. Spectrally resolved photoluminescence demonstrates energy-dependent lifetimes, with radiative rates 10–20 times faster than those of their PbX analogues in the same spectral window. Coupled with their high quantum yield, midgap emission HgX dots on HgX NPLs provide a potential platform for novel optoelectronics in the SWIR.

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

Auger Recombination Lifetime Scaling for Type I and Quasi-Type II Core/Shell Quantum Dots

Having already achieved near-unity quantum yields, with promising properties for light-emitting diode, lasing, and charge separation applications, colloidal core/shell quantum dots have great technological potential. The shell thickness and band alignment of the shell and core materials are known to influence the efficiency of these devices. In many such applications, improving the efficiency requires a deep understanding of multiexcitonic states. In this paper, we elucidate the shell thickness and band alignment dependencies of the biexciton Auger recombination lifetime for quasi-type II CdSe/CdS and type I CdSe/ZnS core/shell quantum dots. We find that the biexciton Auger recombination lifetime increases with the total nanocrystal volume for quasi-type II CdSe/CdS core/shell quantum dots and is independent of the shell thickness for type I CdSe/ZnS core/shell quantum dots. To perform these calculations and compute Auger recombination lifetimes, we developed a low-scaling approach based on the stochastic resolution of identity. The numerical approach provided a framework for studying the scaling of the biexciton Auger recombination lifetimes in terms of the shell thickness dependencies of the exciton radii, Coulomb couplings, and density of final states in quasi-type II CdSe/CdS and type I CdSe/ZnS core/shell quantum dots.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗