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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

Design principles for energy transfer in the photosystem II supercomplex from kinetic transition networks

Photosystem II (PSII) has the unique ability to perform water-splitting. With light-harvesting complexes, it forms the PSII supercomplex (PSII-SC) which is a functional unit that can perform efficient energy conversion, as well as photoprotection, allowing photosynthetic organisms to adapt to the naturally fluctuating sunlight intensity. Achieving these functions requires a collaborative energy transfer network between all subunits of the PSII-SC. In this work, we perform kinetic analyses and characterise the energy landscape of the PSII-SC with a structure-based energy transfer model. With first passage time analyses and kinetic Monte Carlo simulations, we are able to map out the overall energy transfer network. We also investigate how energy transfer pathways are affected when individual protein complexes are removed from the network, revealing the functional roles of the subunits of the PSII-SC. In addition, we provide a quantitative description of the flat energy landscape of the PSII-SC. We show that it is a unique landscape that produces multiple kinetically relevant pathways, corresponding to a high pathway entropy. These design principles are crucial for balancing efficient energy conversion and photoprotection.

59 BASIC BIOLOGICAL SCIENCES

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Charge Separation at Organic Interfaces with Near-Zero Energy Offset: A Step toward Designing Inorganic-like Organic Semiconductors

For organic semiconductors, it is often presumed that an energy level offset at the donor–acceptor (D-A) interface is required to provide the driving force for charge separation (CS). This energy level offset unavoidably leads to a voltage loss in organic photovoltaics. In this work, by using zinc phthalocyanine (ZnPc) and fluorinated zinc phthalocyanine (F 4 ZnPc) as a model D/A interface, we found that spontaneous CS, with an enthalpy increase of ∼0.3–0.4 eV, can occur even with an interfacial energy offset as small as ∼0.1 eV. This enthalpy-increase CS process is driven by entropy. The entropic driving force can be enhanced by two factors: (1) a point-like spatial contact between the delocalized electron and hole wave function in the charge transfer exciton; (2) a small band bending near the interface originating from long-range electrostatic interaction. Our work demonstrates that effective CS can occur at interfaces with a near-zero energy level offset, which means that the energy loss at the D/A interface can be avoided.

36 MATERIALS SCIENCE

Direct-bonded diamond membranes for heterogeneous quantum and electronic technologies

Diamond has superlative material properties for a broad range of quantum and electronic technologies. However, heteroepitaxial growth of single crystal diamond remains limited, impeding integration and evolution of diamond-based technologies. Here, we directly bond single-crystal diamond membranes to a wide variety of materials including silicon, fused silica, sapphire, thermal oxide, and lithium niobate. Our bonding process combines customized membrane synthesis, transfer, and dry surface functionalization, allowing for minimal contamination while providing pathways for near unity yield and scalability. We generate bonded crystalline membranes with thickness as low as 10 nm, sub-nm interfacial regions, and nanometer-scale thickness variability over 200 by 200 μm 2 areas. We measure spin coherence times T 2 for nitrogen vacancy centers in 150 nm-thick bonded membranes of up to 623 ± 21 μs, suitable for advanced quantum applications. We demonstrate multiple methods for integrating high quality factor nanophotonic cavities with the diamond heterostructures, highlighting the platform versatility in quantum photonic applications. Furthermore, we show that our ultra-thin diamond membranes are compatible with total internal reflection fluorescence (TIRF) microscopy, which enables interfacing coherent diamond quantum sensors with living cells while rejecting unwanted background luminescence. The processes demonstrated herein provide a full toolkit to synthesize heterogeneous diamond-based hybrid systems for quantum and electronic technologies.

color center

Diameter-dependent multiple proton jumps dictate hydronium and hydroxide transport in carbon nanotubes

Nanofluidic channels impose extreme confinement on water, giving rise to unusual transport phenomena of the liquid. However, how the transport of hydroxide and hydronium ions is influenced by such confinement is still not fully understood. This study employs machine learning-accelerated simulations, based on the SCAN density functional, to investigate proton transfer dynamics in CNTs of varying diameters (0.8 nm to 2.8 nm). The extreme confinement of water inside a 0.8 nm CNT not only enhances the probability of multiple consecutive proton jumps, but also reverses the relative diffusion coefficient of hydronium and hydroxide ions in bulk water. In CNTs with diameters larger than 0.8 nm, hydronium diffuses slightly faster than in bulk water, whereas hydroxide diffusion slows because of its localization near CNT walls, hindering multiple proton jumps. This work highlights the significant impact of nanoscale confinement on proton transfer dynamics, with implications for designing nanoscale systems with controlled proton transport.

Chemistry

Fluctuating charge-density-wave correlations in the three-band Hubbard model

The high-temperature superconducting cuprates host unidirectional spin- and charge-density-wave orders that can intertwine with superconductivity in nontrivial ways. While the charge components of these stripes have now been observed in nearly all cuprate families, their detailed evolution with doping varies across different materials and at high and low temperatures. We address this problem using nonperturbative determinant quantum Monte Carlo calculations for the three-band Hubbard model. Using an efficient implementation, we can resolve the model’s fluctuating spin and charge modulations and map their evolution as a function of the charge transfer energy and doping. We find that the incommensurability of the charge modulations is decoupled from the spin modulations and decreases with hole doping, consistent with experimental measurements at high temperatures. These findings support the proposal that the high-temperature charge correlations are distinct from the intertwined stripe order observed at low-temperature and in the single-band Hubbard model.

42 ENGINEERING

𝐵 → 𝜌⁢ℓ⁢$\bar{v}$ Resonance Form Factors from 𝐵→ 𝜋⁢𝜋⁢ℓ⁢$\bar{v}$ in Lattice QCD

The decay 𝐵 → 𝜌⁢ℓ⁢$\bar{v}$ is an attractive process for determining the magnitude of the smallest Cabibbo-Kobayashi-Maskawa matrix element, |𝑉 𝑢⁢𝑏 |, and can provide new insights into the origin of the long-standing exclusive-inclusive discrepancy in determinations of this standard-model parameter. This requires a nonperturbative QCD calculation of the 𝐵 → 𝜌 form factors 𝑉, 𝐴 0 , 𝐴 1 , and 𝐴 12 . The unstable nature of the 𝜌 resonance has prevented precise lattice QCD calculations of these form factors to date. Here, we present the first lattice QCD calculation of the 𝐵 → 𝜌 form factors in which the 𝜌 is treated properly as a resonance in 𝑃-wave 𝜋⁢𝜋 scattering. To this end, we use the Lellouch-Lüscher finite-volume formalism to compute the 𝐵 → 𝜋⁢𝜋 form factors as a function of both momentum transfer and 𝜋⁢𝜋 invariant mass, and then analytically continue to the 𝜌 resonance pole. This calculation is performed with 2 + 1 dynamical quark flavors at a pion mass of approximately 320 MeV, and demonstrates a clear path toward results at the physical point.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

Linking leaf dark respiration to leaf traits and reflectance spectroscopy across diverse forest types

Leaf dark respiration (R dark ), an important yet rarely quantified component of carbon cycling in forest ecosystems, is often simulated from leaf traits such as the maximum carboxylation capacity (V cmax ), leaf mass per area (LMA), nitrogen (N) and phosphorus (P) concentrations, in terrestrial biosphere models. However, the validity of these relationships across forest types remains to be thoroughly assessed. Here, in this study, we analyzed R dark variability and its associations with V cmax and other leaf traits across three temperate, subtropical and tropical forests in China, evaluating the effectiveness of leaf spectroscopy as a superior monitoring alternative. We found that leaf magnesium and calcium concentrations were more significant in explaining cross-site R dark than commonly used traits like LMA, N and P concentrations, but univariate trait–R dark relationships were always weak (r 2 ≤ 0.15) and forest-specific. Although multivariate relationships of leaf traits improved the model performance, leaf spectroscopy outperformed trait–R dark relationships, accurately predicted cross-site R dark (r 2 = 0.65) and pinpointed the factors contributing to R dark variability. Our findings reveal a few novel traits with greater cross-site scalability regarding R dark , challenging the use of empirical trait–R dark relationships in process models and emphasize the potential of leaf spectroscopy as a promising alternative for estimating R dark , which could ultimately improve process modeling of terrestrial plant respiration.

59 BASIC BIOLOGICAL SCIENCES

Directed self-assembly of block copolymers for high-precision patterning in the era of extreme ultraviolet lithography

Extreme ultraviolet (EUV) lithography enables unprecedented resolution in semiconductor patterning but faces critical challenges in developing resist materials that achieve high-precision at economically viable throughput. Directed self-assembly (DSA) of block copolymers (BCPs) offers a promising solution for pattern rectification by leveraging thermodynamically determined domain structures to decouple BCP pattern quality from the imperfect original lithographic pattern. This prospective presents an overview of recent progress on the EUV + DSA strategy, covering advances in BCP material design, processing, metrology, and pattern transfer. We highlight recent advances in high-χ BCPs with perpendicular orientation and domain spacings compatible with EUV dimensions, leveraging A-b-(B-r-C) architectures. We also discuss progress in chemical pre-pattern fabrication using both positive- and negative tone resists, along with processing strategies to minimize defects and roughness based on BCP thermodynamics and assembly kinetics. We further examine metrology platforms for characterizing the thermodynamics of BCP materials and quantifying the size and shape of BCP domains. Lastly, we review pattern transfer strategies for generating functional inorganic masks suitable for semiconductor manufacturing. Together, these advances highlight the potential of DSA to complement EUV lithography, offering a pathway to address critical challenges in achieving high-precision patterning for the semiconductor industry.

Lee, Kyunghyeon [Univ. of Chicago, IL (United Stat

Data Files for P. Mai et al., "Fluctuating charge-density-wave correlations in the three-band Hubbard model" (2024)

The high-temperature superconducting cuprates host unidirectional spin- and charge-density-wave orders that can intertwine with superconductivity in nontrivial ways. While the charge components of these stripes have now been observed in nearly all cuprate families, their detailed evolution with doping varies across different materials and at high and low temperatures. We address this problem using nonperturbative determinant quantum Monte Carlo calculations for the three-band Hubbard model. Using an efficient implementation, we can resolve the model’s fluctuating spin and charge modulations and map their evolution as a function of the charge transfer energy and doping. We find that the incommensurability of the charge modulations is decoupled from the spin modulations and decreases with hole doping, consistent with experimental measurements at high temperatures. These findings support the proposal that the high-temperature charge correlations are distinct from the intertwined stripe order observed at low-temperature and in the single-band Hubbard model.

cuprates

Delocalized Excitation Transfer in Open Quantum Systems with Long-Range Interactions

The interplay between coherence and system-environment interactions is at the basis of a wide range of phenomena, from quantum information processing to charge and energy transfer in molecular systems, biomolecules, and photochemical materials. In this work, we use a Frenkel exciton model with long-range interacting qubits coupled to a damped collective bosonic mode to investigate vibrationally assisted transfer processes in donor-acceptor systems featuring internal substructures analogous to light-harvesting complexes. We find that certain delocalized excitonic states maximize the transfer rate and that the entanglement is preserved during the dissipative transfer over a wide range of parameters. We investigate the reduction in transfer caused by static disorder, white noise, and finite temperature and study how transfer efficiency scales as a function of the number of dimerized monomers and the component number of each monomer, finding which excitonic states lead to optimal transfer. Finally, we provide a realistic experimental setting to realize this model in analog trapped-ion quantum simulators. Analog quantum simulation of systems comprising many and increasingly complex monomers could offer valuable insights into the design of light-harvesting materials, particularly in the nonperturbative intermediate parameter regime examined in this study, where classical simulation methods are resource intensive.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC

Nuclear–Electronic Orbital General Rate Theory: Predicting Hydrogen Kinetic Isotope Effects in the Deep Tunneling Regime

Hydrogen transfer is a critical component of many chemical and biological processes. The ratio of rate constants for hydrogen and deuterium transfer defines the H/D kinetic isotope effect (KIE), which is a powerful tool for elucidating hydrogen transfer mechanisms. Interpretation of experimental H/D KIEs relies on accurate and affordable computational methods. However, due to their light mass, hydrogen and deuterium can undergo tunneling, which is challenging to describe in multidimensional molecular systems. Herein, we introduce the nuclear–electronic orbital general rate theory (NEO-GRT), which enables the efficient prediction of H/D KIEs based on full-dimensional molecular quantum chemistry calculations. The NEO-GRT approach describes the hydrogen transfer rate constant with a general expression that spans the vibrationally adiabatic and nonadiabatic hydrogen tunneling regimes. The input quantities are computed using NEO density functional theory, which treats the transferring hydrogen or deuterium nucleus quantum mechanically on the same level as the electrons. We investigate two intramolecular proton transfer reactions in organic molecules at temperatures down to 50 K to evaluate the performance of NEO-GRT by comparison to transition state theory and ring-polymer instanton theory. The KIEs computed with NEO-GRT agree with those calculated using ring-polymer instanton theory for the full-dimensional molecular systems at the same level of electronic structure theory. This agreement indicates that NEO-GRT captures the deep hydrogen tunneling effects, in contrast to transition state theory, which neglects such effects. Given its relatively low computational cost, NEO-GRT is a promising approach for predicting H/D KIEs in large organic and organometallic systems.

Hydrogen

Dual-function lignin monomers enable high-performance graphene electrodes via interface confinement and proton transfer enhancement

Graphene oxide (GO)-based energy storage faces dual bottlenecks: unsustainable reduction methods and sluggish proton transfer kinetics. Here, we introduce a groundbreaking green strategy using lignin-derived vanillyl alcohol (VA) as a dual-function monomer to simultaneously address these challenges. By thermally annealing GO/VA films at mild temperatures (<100 °C), VA triggers an interface-confined reduction of GO while self-polymerizing into redox-active oligomers (P-VA) that intercalate between graphene layers. This dual role-reducing agent and proton highway enables a 3D conductive network with minimized graphene restacking, abundant redox sites, and rapid H + transport pathways. Density Functional Theory (DFT) reveals how P-VA optimizes proton dynamics, while the resulting rGO-P-VA4-T90 electrode achieves a record volumetric capacitance of 311.1F/cm 3 (777.8F/cm 2 ) and retains 87.8 % capacity after 10,000 cycles. Flexible solid-state supercapacitors deliver 94.2 μWh/cm 2 energy density at 63.8 μW/cm 2 , rivaling state-of-the-art devices. Furthermore, this work redefines sustainable graphene engineering, merging biomass valorization with high-performance energy storage in a scalable, eco-friendly paradigm.

Graphene oxide reduction

Mechanisms and Energetics of CO 2 Chemisorption in Choline-Based Eutectic Solvents

Understanding the influences of proton sharing and hydrogen transfer in amine and hydroxyl functionalized eutectic solvents is important for tuning CO 2 binding as they relate to the chemisorption capacity and energetics of solvent regeneration in carbon capture. In this study, we examine how the CO 2 binding mechanism and energetics vary in eutectic solvents composed of choline-based hydrogen-bond acceptors (HBAs) with amine and hydroxyl moieties and ethylene glycol (EG), propylene glycol (PG), 1,2-butanediol (BD), and monoethanolamine (MEA)-type hydrogen-bond donors (HBDs), through absorption–desorption experiments and spectral analysis, supported with density functional theory (DFT) calculations. While the HBD-CO 2 complex is the major and the thermodynamically more favored product of absorption in all of the examined eutectic solvents, this complexation is only possible proceeding a proton transfer from HBD to the HBA in diol-based systems (EG, PG, BD). The interplay between HBA-CO 2 and HBD-CO 2 speciation is governed by the HBD concentration, basicity, and steric effects, with increased HBD-CO 2 interactions in the presence of smaller HBDs (size: BD > PG > EG). On the other hand, in MEA-based systems, CO 2 readily binds to the amine followed by a proton transfer from the amine to the HBA as confirmed by DFT calculations. In this way, the MEA-CO 2 chemisorption capacities exceeded that of the conventional amine (up to 0.93 mol of CO 2 per mol of MEA versus 0.5). Furthermore, the increase in CO 2 capacities and enhanced binding in eutectics including MEA or the more basic HBAs also resulted in regeneration temperatures of 70 to 60 °C with calculated reaction energies of −82 to −57 kJ/mol, compared to 50 °C for others with weaker binding, following CO 2 absorption at 25 °C.

absorption

Edge dislocation mediated anomalous charge transfer in face centered cubic high entropy alloys

The charge transfer in alloys dictates their structural and functional properties. The presence of the line defect can influence the charge transfer characteristics in alloys. The edge dislocation-volume misfit interaction in high entropy alloys is a critical area of interest concerning the development of accurate solid solution strengthening models for these materials. The evolution of the volume misfit of atoms is either studied empirically using Vegard's law or mechanistically using \emph{ab initio} calculations, without considering the effect of edge dislocation on charge transfer explicitly. In this work, we show the influence of edge dislocation on the charge transfer in CoCrFeMnNi, CoCrNi and CoNi using large-scale \emph{ab initio} calculations. The anomalous charge transfer characteristics, in terms of deviations from electronegativity trends, are demonstrated, which are dictated by electronegativity equalisation rather than pair-atom interactions. The deviation of atomic volume in the compressive and tensile stress regions of the edge dislocation is rationalised in terms of anomalous magneto-volume fluctuations in such alloys.

Ghosh, Swarnava [ORNL] (ORCID:0000000338005264)

Trade-offs among restored ecosystem functions are context-dependent in Mediterranean-type regions

Global biodiversity hotspots, including Mediterranean-type ecosystems worldwide, are highly threatened by global change that alters biodiversity, ecosystem functions, and services. Some restoration activities enhance ecosystem functions by reintroducing plant species based on known relationships between plant traits and ecosystem processes. Achieving multiple functions across different site conditions, however, requires understanding how abiotic factors like climate and soil, along with plant assemblages, influence ecosystem functions, including their trade-offs and synergies. We used the ModEST ecosystem simulation model, which integrates carbon, water, and nutrient processes with plant traits, to assess the relationships between restored plant assemblages and ecosystem functions in Mediterranean-type climates and soils. We investigated whether maximised carbon increment, water use efficiency, and nitrogen use efficiency, along with their trade-offs and synergies, varied across different abiotic contexts. Further, we asked whether assemblages that maximised functions varied across environments and among these functions. We found that maximised ecosystem carbon increment and nitrogen use efficiency occurred under moist, warm conditions, while water use efficiency peaked under drier conditions. Generally, the assemblage that maximised one function differed from those for other maximised functions. Synergies were rare, except between water and nitrogen use efficiencies in loam soils across most climates. Trade-offs among maximised functions were common, varying in strength with abiotic context and plant assemblages, and were more pronounced in sandy loam soils compared to clay-rich soils. Our findings suggest that due to variation in abiotic conditions within and across Mediterranean-type regions at the global scale, site-specific plant assemblages are required to maximise ecosystem functions. Thus, lessons from a single site cannot be transferred to another site, even where the same plant functional types are available for restoration. Our simulation results offer valuable insights into potential ecosystem performance under specific abiotic conditions following restoration with particular plant functional types, thereby informing local restoration efforts.

54 ENVIRONMENTAL SCIENCES

Pick-and-Place Transfer of Arbitrary-Metal Electrodes for van der Waals Device Fabrication

Van der Waals electrode integration is a promising strategy to create nearly perfect interfaces between metals and 2D materials, with advantages such as eliminating Fermi-level pinning and reducing contact resistance. However, the lack of a simple, generalizable pick-and-place transfer technology has greatly hampered the wide use of this technique. Here, we demonstrate the pick-and-place transfer of prefabricated electrodes from reusable polished hydrogenated diamond substrates without the use of any sacrificial layers due to the inherent low-energy and dangling-bond-free nature of the hydrogenated diamond surface. The technique enables transfer of arbitrary-metal electrodes and an electrode array, as demonstrated by successful transfer of eight different elemental metals with work functions ranging from 4.22 to 5.65 eV. We also demonstrate the electrode array transfer for large-scale device fabrication. The mechanical transfer of metal electrodes from diamond to van der Waals materials creates atomically smooth interfaces with no interstitial impurities or disorder, as observed with cross-section high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy. As a demonstration of its device application, we use the diamond transfer technique to create metal contacts to monolayer transition metal dichalcogenide semiconductors with high-work-function Pd, low-work-function Ti, and semimetal Bi to create n- and p-type field-effect transistors with low Schottky barrier heights. We also extend this technology to air-sensitive materials (trilayer 1T’ WTe 2 ) and other applications such as ambipolar transistors, Schottky diodes, and optoelectronics. This highly reliable and reproducible technology paves the way for new device architectures and high-performance devices.

2D materials