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At least 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Rationalizing energy level alignment by characterizing Lewis acid/base and ionic interactions at printable semiconductor/ionic liquid interfaces

Charge transfer and energy conversion processes at semiconductor/electrolyte interfaces are controlled by local electric field distributions, which can be especially challenging to measure. Furthermore, we leverage the low vapor pressure and vacuum compatibility of ionic liquid electrolytes to undertake a layer-by-layer, ultra-high vacuum deposition of a prototypical ionic liquid EMIM + (1-ethyl-3-methylimidazolium) and TFSI – (bis(trifluoromethylsulfonyl)-imide) on the surfaces of different electronic materials. We consider a case-by-case study between a standard metal (Au) and four printed electronic materials, where interfaces are characterized by a combination of X-ray and ultraviolet photoemission spectroscopies (XPS/UPS). For template-stripped gold surfaces, we observe through XPS a preferential orientation of the TFSI anion at the gold surface, enabling large electric fields (~10 8 eV m –1 ) within the first two monolayers detected by a large surface vacuum level shift (0.7 eV) in UPS.

14 SOLAR ENERGY↗
NASA NTRS1995

Modeling and numerical simulation of microwave pulse propagation in air breakdown environment

It is shown that ionization occurs wherever the field intensity of the pulse exceeds the local breakdown threshold field of the background air. The produced plasma then attenuates the pulse and gives rise to a tail erosion phenomenon that plays the primary role in limiting the energy transfer of the pulse from source to destination. A theoretical model describing the propagation of an intense microwave pulse in an air breakdown environment is developed that includes the possible focusing effect introduced by either using phase array antennas or the other arrangements. The self-consistent description of the propagation process is provided by a set of two modal equations. These include a continuity equation (Poynting's equation) for the energy density of the pulse and a rate equation of the electron density. A forward wave approximation is used to simplify Poynting's equation, and a semiempirical formula is used for the ionization frequency, nu(sub i). This frequency provides the coupling between the two modal equations, and is used to express the electron rate equation explicitly. In terms of the relevant parameters of the atmosphere, these two equations are normalized for numerical analysis of pulse propagation in the atmosphere. The dependencies of the propagation characteristics of the pulse on intensity, frequency, width, and shape of the pulse are determined. The numerical simulations lead to a useful empirical relation p(exp 3)w = alpha = constant, where p and w are the incident power and width of the pulse and alpha depends on the percentage of pulse energy transferred from the source point to a destined position. The density distribution of the pulse's self-generated plasma is also evaluated. The results also show that for ionization caused by a single unfocused microwave pulse transmitted upwards from the ground, the maximum electron density produced at, for example, 50 km altitude is limited by the tail erosion effect to below 10(exp 6) cm(exp -3). Repetitive pulse and focused beam approaches are also examined. Both approaches can increase the maximum electron density by no more than an order of magnitude. A scheme using two obliquely propagating pulses intersecting at the destined height, e.g. 50 km, is considered. It is shown that the electron density generated at the lowest intersecting position can easily reach a value of 6.6 x 10(exp 8) cm(exp -3), which is considered to be high enough for artificial ionospheric mirror (AIM) application.

Kim, J.↗
DOE OSTI2025

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Epitaxial growth of highly symmetrical branched noble metal-semiconductor heterostructures with efficient plasmon-induced hot-electron transfer

Epitaxial growth is one of the most commonly used strategies to precisely tailor heterostructures with well-defined compositions, morphologies, crystal phases, and interfaces for various applications. However, as epitaxial growth requires a small interfacial lattice mismatch between the components, it remains a challenge for the epitaxial synthesis of heterostructures constructed by materials with large lattice mismatch and/or different chemical bonding, especially the noble metal-semiconductor heterostructures. Here, we develop a noble metal-seeded epitaxial growth strategy to prepare highly symmetrical noble metal-semiconductor branched heterostructures with desired spatial configurations, i.e., twenty CdS (or CdSe) nanorods epitaxially grown on twenty exposed (111) facets of Ag icosahedral nanocrystal, albeit a large lattice mismatch (more than 40%). Importantly, a high quantum yield (QY) of plasmon-induced hot-electron transferred from Ag to CdS was observed in epitaxial Ag-CdS icosapods (18.1%). This work demonstrates that epitaxial growth can be achieved in heterostructures composed of materials with large lattice mismatches. The constructed epitaxial noble metal-semiconductor interfaces could be an ideal platform for investigating the role of interfaces in various physicochemical processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Surface oxygenation induced strong interaction between Pd catalyst and functional support for zinc–air batteries

Employing the strong metal-support interaction (SMSI) effect for promoting the catalyst's activity toward the oxygen reduction reaction (ORR) is promising due to the electronic structure optimization and high utilization efficiency of platinum group metal (PGM) catalysts. Metal oxides as alternative supports for PGMs facilitate intrinsic activity and improve durability as compared to conventional carbon supports. However, the restricted mass and electron transfer at the metal/support interface need to be addressed. Herein, to strengthen the interaction at the metal/support interfaces and improve the utilization efficiency of PGM, an ultralow loading of Pd was embedded in a surface-oxygenated PdNiMnO porous film. The Mn-doping was designed to promote surface oxygenation using a facile anodization process that created sufficiently exposed interfaces between Pd and the support, strengthening the SMSI effects at the Pd/oxygenated support interface for enhancing ORR performance. Furthermore, the Ni-containing oxygenated catalyst served as both the active component for the oxygen evolution reaction (OER) and the functional support for stabilizing Pd, making PdNiMnO a bifunctional catalyst for zinc–air flow batteries (ZAFB). As a proof-of-concept, the ZAFB (PdNiMnO) shows a maximal power density of 211.6 mW cm –2 and outstanding cycling stability for over 2000 h with a minimal voltage gap of 0.69 V at a current density of 10 mA cm –2 , superior to the state-of-the-art catalysts.

25 ENERGY STORAGE↗
DOE OSTI2024

Radiation transfer in the spectra of short-pulse laser-heated targets

The conditions in laser-produced plasmas are frequently determined with x-ray spectroscopy by comparing calculated to measured spectra. Line spectra from K-shell transitions of low- to mid-atomic number elements are most often used since the important physical processes are well understood and reliable spectra can be readily measured and calculated. Radiation transfer effects due to large optical depths of strong lines can influence the spectra. In this work, the effects of radiation transfer on the emission spectra of short-laser pulse-heated targets are studied. The possible errors made in inferring electron temperature by not including radiation transfer are quantified. The inclusion of radiative transfer in spectral calculations improves the accuracy of typical temperature diagnostics and allows the use of strong lines for diagnostics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Coherent Transfer of Lattice Entropy via Extreme Nonlinear Phononics in Metal Halide Perovskites

Entropy transfer in metal halide perovskites, characterized by significant lattice anharmonicity and low stiffness, underlies the remarkable properties observed in their optoelectronic applications, ranging from solar cells to lasers. The conventional view of this transfer involves stochastic processes occurring within a thermal bath of phonons, where the lattice arrangement and energy flow from higher- to lower-frequency modes. Here, we unveil a comprehensive chronological sequence detailing a conceptually distinct coherent transfer of entropy in a prototypical perovskite CH 3 NH 3 Pbl 3 . The terahertz periodic modulation imposes vibrational coherence into electronic states, leading to the emergence of mixed (vibronic) quantum beat between approximately 3 and 0.3 THz. We highlight a well-structured bidirectional time-frequency transfer of these diverse phonon modes, each developing at different times and transitioning from high to low frequencies from 3 to 0.3 THz, before reversing direction and ascending to around 0.8 THz. First-principles molecular dynamics simulations disentangle a complex web of coherent-phononic coupling pathways and identify the salient roles of the initial modes in shaping entropy evolution at later stages. Capitalizing on coherent entropy transfer and dynamic anharmonicity presents a compelling opportunity to exceed the fundamental thermodynamic (Shockley-Queisser) limit of photoconversion efficiency and to pioneer novel optoelectronic functionalities. Published by the American Physical Society 2024

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Dissimilar metal joining of Ti-6Al-4V and Inconel 625

The dissimilar joining of Ti-6Al-4V and Inconel 625 by using a suitable interlayer shows potential design flexibility by avoiding the brittle intermetallic phases from direct welding. These phases include NiTi , NiTi 2 , and Ni 3 Ti . The objective of this work is to facilitate laser welding of Ti-6Al-4V and Inconel 625 through a vanadium interlayer to form an intermetallic free, strong, and corrosion resistant joint. Vanadium was chosen based on binary phase diagram solubilities, literature, and theoretical CalPhaD calculations in PanDat. Laser welding was systematically explored from based on beam mode, offset, power, and scan speed. Varied parameters include laser power from 325 to 650 watts, laser scan speed from 80 to 160 in/min, and beam offset up to a ¼ of the beam diameter. Parameters were chosen based on previous dissimilar joining research and those found in the literature. Metallography, including optical and scanning electron microscopy, was used to analyze the weld chemical composition, grain structure, and defects through both the fusion and heat affected zones. The results and discussion will examine the relationship between process parameters, microstructure, and observed weld defects. Our findings will not only assess the weldability of vanadium and Inconel 625 but also establish a transferable framework for studying other dissimilar material combinations, providing valuable insights for future research in this field.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Restriction-In-Motion of Surface Ligands Enhances Photoluminescence of Quantum Dots - Experiment and Theory

Here the relationship between emission and ligand restriction of a series of ZnSe/ZnS quantum dots (QDs) encapsulated in nanoparticles is investigated systematically via experiments and quantum theory. The QDs have a ZnSe core and a ZnS shell, capped with hydrophobic ligands (triotylphosphine oxide/hexadecylamine), allowing them to be entrapped in a model biomembrane, bicelle, made of zwitterionic dipalmitoyl and dihexanoyl phosphatidylcholines and charged dipalmitoyl phosphatidylglycerol. Enhanced photoluminescence is observed upon encapsulation, depending on the QD-to-lipid ratio. Transmission electron microscopy and small-angle X-ray scattering confirm that QDs are preferably situated at the rim of bicellar discs. A simplified quantum dissipation heat-bath theory is proposed to correlate the enhancement with slower nonradiative processes caused by the restriction-in-motion (RIM) of the surface ligands. However, Fõrster resonance energy transfer due to QD aggregation counteracts the effect.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Numerical analysis of coalescence-induced bubble departure for enhanced boiling heat transfer

Boiling heat transfer plays a crucial role in a wide range of applications, such as power generation, refrigeration, electronics cooling, and pharmaceutics. Among the various factors that influence boiling heat transfer, the dynamics of vapor bubble nucleation, growth, and departure from the heated surface stand out as particularly important. An emerging phenomenon that can promote the departure of bubbles smaller than the Fritz diameter is coalescence-induced departure. If the dynamics of this process are fully understood, then surfaces can be engineered to promote faster bubble departure and substantially increase the performance of boiling heat transfer. Further, this work expands on published results by presenting a detailed numerical analysis of bubble coalescence and departure for a range of initial bubble diameters and size ratios between coalescing bubbles. Analysis of the results is focused on explaining how the release of surface energy and bubble surface dynamics lead to bubble departure, as well as fundamentally distinguishing capillary–inertial jumping and buoyant–inertial departure mechanisms across different bubble sizes and size ratios. The results show that both the initial sizes of the coalescing bubbles and the ratio between their sizes can determine whether the merged bubble will leave the surface through capillary–inertial jumping or buoyant departure. Below a certain bubble size, the release of surface energy by the merger is not sufficient to propel the merged bubble from the surface.

42 ENGINEERING↗
DOE OSTI2022

Chemical Challenges that the Peroxide Dianion Presents to Rechargeable Lithium–Air Batteries

Understanding the fundamental redox reactions and processes that occur in lithium–air and, more generally, metal–air batteries is important to the progress of this promising energy-storage technology. Knowledge of the chemistry of the peroxide dianion, O 2 2– , is especially crucial, as the dianion is at the nexus of the charge/discharge cycle of lithium–air batteries. The intrinsic electron transfer properties and redox chemistry of peroxide dianion are poorly defined because it is difficult to isolate the dianion free of protons and metal ions. We review the results of (i) the electron transfer kinetics and (ii) the redox reaction chemistry of isolated peroxide dianion encapsulated within the cavity of a hexacarboxamide cryptand. With regard to the former, electron transfer kinetics measurements provide fundamental Marcus parameters that will be useful for models that seek to disentangle the precise contributions of Li + ion-coupled electron transfer, electron transfer across the Li 2 O 2 solid particle interface, and charge hopping among Li 2 O 2 particles. With regard to the latter, an underappreciated chemistry of peroxide dianion with CO 2 produces peroxymonocarbonate (OOCO 2 2– ) and peroxydicarbonate (O 2 COOCO 2 2– ). An autocatalytic cycle will lead to oxidative degradation of traditional organic electrolytes and other vulnerable cell components employed in lithium–air batteries. Furthermore, this peroxycarbonate-derived chemistry, in addition to more commonly recognized solution-based oxidation chemistry, will need to be mitigated to realize the long-term cyclability of rechargeable lithium–air batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Resistive Switching of Spinel Li 4 Ti 5 O 12 Lithium-Ion Battery Material for Neuromorphic Computing

The rapid rise of AI has exposed significant limitations in conventional Von Neumann computing architecture, particularly in regard to speed and energy efficiency. To address these challenges, researchers are exploring a brain-inspired neuromorphic architecture that mimics biological neural networks, enabling massive parallel processing with reduced power consumption for complex AI computational demands. Recent interest has focused on utilizing battery electrodes and solid electrolyte materials for their resistive switching properties in developing a neuromorphic architecture. These properties are precisely tuned through local- and bulk-level chemical composition modifications via voltage bias stimuli. In this study, we demonstrate fabricating a three-terminal lithium-ion electrochemical transistor based on lithium titanium oxide (Li 4 Ti 5 O 12 ), a popular lithium-ion battery anode material. We deposited and characterized LTO thin films using RF sputtering, demonstrating a 6 orders of magnitude increase in electronic conductivity upon lithiation, with conductivity plateauing after 20% lithiation. Density functional theory calculations revealed transformation from the insulating to conducting state, supported by experimental characterization through X-Ray Photoelectron Spectroscopy (XPS) and Direct Current (DC) polarization analyses. The fabricated transistor consisted of LTO as the channel layer, gold as source/drain terminals, lithium phosphorus oxynitride (LiPON) as the lithium-ion conductor, and copper as the gate terminal. The device exhibited clear hysteresis in transfer characteristics due to lithium insertion/extraction processes. Long-term potentiation (LTP) and long-term depression (LTD) measurements showed an asymmetric ratio of 1.425 and maximum/minimum conductance ratio of 7.83. When implemented in a deep neural network (DNN) for MNIST handwritten digit recognition, the device achieved 92.03% accuracy over 20 training epochs. Detailed transport mechanism analysis revealed the crucial role of oxygen vacancies and interface effects in device operation. Our preliminary findings establish LTO-based lithium-ion electrochemical transistors as promising candidates for energy-efficient neuromorphic computing applications, offering potential solutions to traditional Von Neumann architecture limitations.

25 ENERGY STORAGE↗
DOE OSTI2025

Photochemical Ligand-Based CO 2 Reduction Mediated by Ruthenium Formyl Species

Here, a new, ligand-based strategy for CO 2 reduction to formate has been demonstrated. This approach relies on the photochemical generation of a coordinatively saturated transient ruthenium metalloformyl species, Ru-CHO, capable of reducing CO 2 to free formate directly. Under this paradigm, a highly reactive radical cation which is capable of facile formal hydrogen atom transfer (HAT) is generated via reductive quenching of an excited-state photosensitizer. Sequential electron transfer (ET) and HAT steps to a ruthenium carbonyl complex subsequently yield the Ru-CHO species, which upon further reduction undergoes fast hydride transfer to CO 2 , producing free formate. High formate selectivity (up to 98%) and impressive catalytic performance (TON ~5300; TOF ~0.1 s -1 ) was observed. Detailed mechanistic studies revealed that the overall process is highly sensitive to the identity of the radical cation, with divergent reactivity observed when HAT thermodynamics are altered. These findings provide new insights into ligand-based hydride transfer mechanisms and establish a foundation for the rational design of selective CO 2 reduction catalysts.

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

New Materials for Photoelectrochemical Energy Conversion

This review concerns light-to-chemical energy conversion, focusing on approaches that could be driven by terrestrial sunlight to produce hydrogen and/or reduce carbon dioxide. Recent advances in photocatalytic (PC) and photoelectrocatalytic (PEC) materials are covered. In both approaches, the electron-hole pairs that are created by photon absorption must travel in specific directions to the sites that mediate multielectron bond making/breaking redox reactions. Thermodynamic requirements for materials stability are described, although some recently discovered materials appear to be exceptions. For PC materials, the importance of rate matching between reduction and oxidation processes and the mass transfer of intermediates and products is emphasized. Surprisingly, metal sulfides appear to be promising for PC carbon dioxide reduction. For PEC materials, recent work elucidating the elementary step mechanism for oxygen evolution on metal oxides and the discovery of chalcogen-based photocathode materials capable of sustained light-driven CO 2 reduction are discussed.

energy conversion↗
DOE OSTI2026

The emergent photophysics and photochemistry of molecular polaritons: a theoretical and computational investigation (Final Technical Report)

When molecules are placed between closely spaced mirrors, they interact strongly with the photons that are trapped between them, generating new quantum states which are no longer exclusively material nor photonic alone, but rather, coherent superpositions of both. These hybrid states are known as molecular polaritons, given that they arise from the strong interaction between the electric field of light and the electrical polarization of the molecules. Recently, experimental advances in nano‐ and microfabrication of molecular polariton architectures have successfully demonstrated their feasibility to control the rate and outcome of a certain class of chemical reactions in condensed phases. Importantly, these reactions proceed in strongly dissipative environments such as liquid solvents and lossy mirrors that allow for photons to escape from their confinement. The purpose of this research is to formulate quantum mechanical theories and computational tools that can elucidate the origin of these intriguing phenomena and simultaneously predict capabilities that this new generation of molecular materials affords. Attention is placed on harnessing polaritons to carry out photophysics and photochemistry that challenge currently existing paradigms, such as the optimization of energy conversion processes in organic solar cell or light‐emitting devices, or unconventional phenomena such as long‐range excitation energy transfer, remote control of chemical reactions, and a new quantum mechanical regime of chemical reactivity due to wavefunction overlaps amongst a large number of molecular polaritons (Bose condensation). This research explores a frontier of Chemistry and Physics where electrons, vibrations, and photons interact strongly with each other to generate emergent behavior that can be creatively exploited to address contemporary challenges in Basic Energy Sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Theoretical prediction of the impact of Auger recombination on charge collection from an ion track

The theoretical analysis presented indicates that Auger recombination can reduce charge collection from very dense ion tracks in silicon devices. It is of marginal importance for tracks produced by 270-MeV krypton, and therefore it is of major importance for ions exhibiting a significantly larger loss. The analysis shows that recombination loss is profoundly affected by track diffusion. As the track diffuses, the density and recombination rate decrease so fast that the linear density (number of electron-hole pairs per unit length) approaches a nonzero limiting value as t approaches infinity. Furthermore, the linear density is very nearly equal to this limiting value in a few picoseconds or less. When Auger recombination accompanies charge transport processes that have much longer time scales, it can be simulated by assigning a reduced linear energy transfer to the ion.

Edmonds, Larry D.↗
DOE OSTI2021

Charge Transfer and Spin Dynamics in a Zinc Porphyrin Donor Covalently Linked to One or Two Naphthalenediimide Acceptors

We report quantum coherence effects on charge transfer and spin dynamics in a system having two degenerate electron acceptors are studied using a zinc 5,10,15-tri(n-pentyI)-20-phenylporphyrin (ZnP) electron donor covalently linked to either one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) electron acceptors using an anthracene (An) spacer, ZnP-An-NDI (1) and ZnP-An-NDI 2 (2), respectively. Following photoexcitation of 1 and 2 in toluene at 295 K, femtosecond transient absorption spectroscopy shows that the electron transfer (ET) rate constant for 2 is about three times larger than that of 1, which can be accounted for by the statistical nature of incoherent ET as well as the electron couplings for the charge separation reactions. In contrast, the rate constant for charge recombination (CR) of 1 is about 25% faster than that of 2. Using femtosecond transient infrared spectroscopy and theoretical analysis, we find that the electron on NDI 2 ∙- in 2 localizes onto one of the two NDIs prior to CR, thus precluding electronically coherent CR from NDI 2 ∙- . Conversely, CR in both 1 and 2 is spin coherent as indicated by the observation of a resonance in the 3* ZnP yield following CR as a function of applied magnetic field, giving spin-spin exchange interaction energies of 2J = 210 and 236 mT, respectively, where the line width of the resonance for 2 is greater than 1. These data show that while CR is a spin-coherent process, incoherent hopping of the electron between the two NDIs in 2, consistent with the lack of delocalization noted above, results in greater spin decoherence in 2 relative to 1.

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

Nonorthogonal Configuration Interaction for Singlet Fission: Beyond the Dimer

Non-orthogonal configuration interaction with fragment calculations are presented for a number of compounds that show singlet fission properties: (i) four perylene-diimide derivatives, (ii) crystalline pentacene and its (B,N)-substituted variant, and (iii) a regular and a distorted stack of three indolonaphthyridine molecules. The electronic couplings between the singlet excitonic states (S 1 ) and the singlet-coupled double triplet (T 1 T 1 ), the so-called singlet fission coupling, were computed from ensembles with two and three molecules, and except for some small deviations when charge transfer states were included, results are virtually the same. Ensembles of three molecules were used to study the mechanisms of triplet separation, double triplet diffusion, and singlet and triplet exciton diffusion. The calculations show that apart from the standard mechanism for the generation of two uncoupled triplet states (S 1 → T 1 T 1 → T 1 ...T 1 ), there are two other possible pathways: the direct generation from the singlet excitonic state (S 1 → T 1 ...T 1 ) and the process in which the excitonic state evolves in a superposition of T 1 T 1 and T 1 ...T 1 states. Furthermore, the electronic coupling for triplet diffusion is in general much smaller than for singlet diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗