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At least 253 records · Page 14

Assessing the effect of regularization on the molecular properties predicted by SCAN and self-interaction corrected SCAN meta-GGA

Recent regularization of the SCAN meta-GGA functional (rSCAN) has simplified the numerical complexities of the SCAN functional, alleviating SCAN's stringent demand on the numerical integration grids to some extent. The regularization of rSCAN, however, results in the breaking of some constraints such as the uniform electron gas limit, the slowly varying density limit, and coordinate scaling of the iso-orbital indicator. Here, we assess the effects of regularization on the electronic, structural, vibrational, and magnetic properties of molecules by comparing the SCAN and rSCAN predictions. The properties studied include atomic energies, atomization energies, ionization potentials, electron affinities, barrier heights, infrared intensities, dissociation and reaction energies, spin moments of molecular magnets, and isomer ordering of water clusters. Our results show that rSCAN requires less dense numerical grids and gives very similar results to those of SCAN for all properties examined with the exception of atomization energies, which are worsened in rSCAN. We also examine the performance of self-interaction-corrected (SIC) rSCAN with respect to SIC-SCAN using the Perdew–Zunger (PZ) SIC method. The PZSIC method uses orbital densities to compute one-electron self-interaction errors and places an even more stringent demand on numerical grids. Our results show that SIC-rSCAN gives marginally better performance than SIC-SCAN for almost all properties studied in this work with numerical grids that are on average half or less as dense as that needed for SIC-SCAN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Switchable client specificity in a dual functional chaperone coordinates light-harvesting complex biogenesis

The proper assembly of light-harvesting complexes (LHCs) is critical for photosynthesis and requires the biogenesis of light-harvesting chlorophylla,b-binding proteins (LHCPs) to be coordinated with chlorophyll (Chl) biosynthesis. The mechanism underlying this coordination is not well understood. Here, we show that a conserved molecular chaperone, chloroplast signal recognition particle 43-kDa protein (cpSRP43), provides a molecular thermostat that helps maintain this coordination. cpSRP43 undergoes a conformational rearrangement between a well-folded closed state and a partially disordered open state. Closed cpSRP43 is dedicated to the biogenesis of LHCPs, whereas open cpSRP43 protects multiple Chl biosynthesis enzymes from heat-induced destabilization. Rising temperature shifts cpSRP43 to the open state, enabling it to protect heat-destabilized Chl biosynthesis enzymes. Our results reveal the molecular basis of a posttranslational mechanism for the thermoadaptation of LHC biogenesis. They also demonstrate how an adenosine triphosphate–independent chaperone uses conformational dynamics to switch its activity and client selectivity, thereby adapting to different proteostatic demands under shifting environmental conditions.

Science & Technology - Other Topics↗

Characterization and Analysis of the Energy-Reporting Accuracy of Connected Devices

Emerging energy-efficient building systems increasingly exhibit greater functionality, often requiring multiple operating modes (e.g. white-tunability for lighting products and data traffic for devices with networked, integrated sensors). This increased functionality makes energy consumption estimates more complex. Given that these functions consume energy, the energy performance of such building systems is dependent on what operating modes they use and how much time they spend in each mode. Devices and systems that can report their own energy consumption mitigate this energy-performance uncertainty. This study explores the energy-reporting accuracy of market-available connected electrical outlets. The study considers two residential-market products (five units each, one outlet per unit) and three commercial-market products (two units each, 18 to 24 outlets per unit) with the ability to report power drawn and/or energy consumed by devices connected to their receptacles. The products were purchased through typical market channels. Pacific Northwest National Laboratory (PNNL) conducted testing in December 2018 at its Connected Lighting Test Bed (CLTB), using a custom-developed test setup and method adapted from industry standards. The setup collected energy-consumption data reported by the outlet devices under test (DUTs) at one-minute intervals and compared that data with measurements taken by a reference meter over a range of test conditions. The residential products reported power draw but not interval or cumulative energy consumption. The commercial products reported both power draw and cumulative energy consumption. Relative reporting error (RRE) was calculated for all measurements, and analysis of the results revealed variations across devices and test conditions. The total number of measurements (50 for each residential product, 60 for each commercial product) offers an appreciable comparison of performance at the make/model level. The average RRE of the residential products derived from reported power draw was -0.02% and -1.20%. The average RRE for two of the three the commercial products derived from reported power draw was worse than those of the residential products (-2.40%, -2.72%, -0.36%). The internal integration of power over time, used to calculate cumulative energy consumption, typically occurs at current and voltage sampling rates much higher than once per minute. This suggests that the average commercial-product RRE derived from reported energy consumption should be very consistent and better than performance based on reported power draw. However, the RRE derived from reported energy consumption varied significantly across the three makes of commercial-market products and was uniformly less accurate than performance based on reported power draw. Subsequent analysis identified a number of root causes for this decrease in performance, most of which were related to reporting resolution. The goals of this study are to generate awareness of building systems capable of reporting their own energy consumption, further interest in the value of energy data for a variety of uses, draw attention to how the accuracy of reported metrics can be characterized, and quantify the performance variation found in marketavailable products. The results of this study and subsequent related work may be relevant to stakeholders in industry-specification and standards-development organizations. The methods this study employs could inform test and measurement procedures and performance classifications for connected outlets, lighting products, and other building systems capable of reporting their own energy consumption. The study concludes with stakeholder recommendations, including the following: • Energy-reporting device and system manufacturers developing products that report energy consumption should characterize the accuracy of reported metrics using a reference meter calibrated by an independent laboratory that was accredited by an ILAC MRA signatory (and whose scope of accreditation explicitly covers energy measurement), and should include this information on product data sheets. • Standards and specification development organizations should develop application-specific performance classifications that end users can understand and relate to their energy-data use needs (e.g., 2% accuracy class for utility streetlight energy billing needs, or 10% accuracy class for ESCO performance verification needs). • Current or potential owners, operators, and specifiers of energy-reporting building systems should rigorously analyze the dependency of current and planned energy-data use cases on accuracy, noting in particular the dependence (or lack thereof) on relative vs. absolute accuracy, and on trueness vs. precision (i.e., repeatability), and should communicate use-case needs to industry standards and specification organizations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Characterization and Analysis of the Energy-Reporting Accuracy of Connected Devices

Emerging energy-efficient building systems increasingly exhibit greater functionality, often requiring multiple operating modes (e.g. white-tunability for lighting products and data traffic for devices with networked, integrated sensors). This increased functionality makes energy consumption estimates more complex. Given that these functions consume energy, the energy performance of such building systems is dependent on what operating modes they use and how much time they spend in each mode. Devices and systems that can report their own energy consumption mitigate this energy-performance uncertainty. This study explores the energy-reporting accuracy of market-available connected electrical outlets. The study considers two residential-market products (five units each, one outlet per unit) and three commercial-market products (two units each, 18 to 24 outlets per unit) with the ability to report power drawn and/or energy consumed by devices connected to their receptacles. The products were purchased through typical market channels. Pacific Northwest National Laboratory (PNNL) conducted testing in December 2018 at its Connected Lighting Test Bed (CLTB), using a custom-developed test setup and method adapted from industry standards. The setup collected energy-consumption data reported by the outlet devices under test (DUTs) at one-minute intervals and compared that data with measurements taken by a reference meter over a range of test conditions. The residential products reported power draw but not interval or cumulative energy consumption. The commercial products reported both power draw and cumulative energy consumption. Relative reporting error (RRE) was calculated for all measurements, and analysis of the results revealed variations across devices and test conditions. The total number of measurements (50 for each residential product, 60 for each commercial product) offers an appreciable comparison of performance at the make/model level. The average RRE of the residential products derived from reported power draw was -0.02% and -1.20%. The average RRE for two of the three the commercial products derived from reported power draw was worse than those of the residential products (-2.40%, -2.72%, -0.36%). The internal integration of power over time, used to calculate cumulative energy consumption, typically occurs at current and voltage sampling rates much higher than once per minute. This suggests that the average commercial-product RRE derived from reported energy consumption should be very consistent and better than performance based on reported power draw. However, the RRE derived from reported energy consumption varied significantly across the three makes of commercial-market products and was uniformly less accurate than performance based on reported power draw. Subsequent analysis identified a number of root causes for this decrease in performance, most of which were related to reporting resolution. The goals of this study are to generate awareness of building systems capable of reporting their own energy consumption, further interest in the value of energy data for a variety of uses, draw attention to how the accuracy of reported metrics can be characterized, and quantify the performance variation found in marketavailable products. The results of this study and subsequent related work may be relevant to stakeholders in industry-specification and standards-development organizations. The methods this study employs could inform test and measurement procedures and performance classifications for connected outlets, lighting products, and other building systems capable of reporting their own energy consumption. The study concludes with stakeholder recommendations, including the following: • Energy-reporting device and system manufacturers developing products that report energy consumption should characterize the accuracy of reported metrics using a reference meter calibrated by an independent laboratory that was accredited by an ILAC MRA signatory (and whose scope of accreditation explicitly covers energy measurement), and should include this information on product data sheets. • Standards and specification development organizations should develop application-specific performance classifications that end users can understand and relate to their energy-data use needs (e.g., 2% accuracy class for utility streetlight energy billing needs, or 10% accuracy class for ESCO performance verification needs). • Current or potential owners, operators, and specifiers of energy-reporting building systems should rigorously analyze the dependency of current and planned energy-data use cases on accuracy, noting in particular the dependence (or lack thereof) on relative vs. absolute accuracy, and on trueness vs. precision (i.e., repeatability), and should communicate use-case needs to industry standards and specification organizations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Functional anatomy of zinc finger antiviral protein complexes

Abstract ZAP is an antiviral protein that binds to and depletes viral RNA, which is often distinguished from vertebrate host RNA by its elevated CpG content. Two ZAP cofactors, TRIM25 and KHNYN, have activities that are poorly understood. Here, we show that functional interactions between ZAP, TRIM25 and KHNYN involve multiple domains of each protein, and that the ability of TRIM25 to multimerize via its RING domain augments ZAP activity and specificity. We show that KHNYN is an active nuclease that acts in a partly redundant manner with its homolog N4BP1. The ZAP N-terminal RNA binding domain constitutes a minimal core that is essential for antiviral complex activity, and we present a crystal structure of this domain that reveals contacts with the functionally required KHNYN C-terminal domain. These contacts are remote from the ZAP CpG binding site and would not interfere with RNA binding. Based on our dissection of ZAP, TRIM25 and KHNYN functional anatomy, we could design artificial chimeric antiviral proteins that reconstitute the antiviral function of the intact authentic proteins, but in the absence of protein domains that are otherwise required for activity. Together, these results suggest a model for the RNA recognition and action of ZAP-containing antiviral protein complexes.

Science & Technology - Other Topics↗

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↗

X-ray nano-holotomography reconstruction with simultaneous probe retrieval

In conventional tomographic reconstruction, the pre-processing step includes flat-field correction, where each sample projection on the detector is divided by a reference image taken without the sample. When using coherent X-rays as a probe, this approach overlooks the phase component of the illumination field (probe), leading to artifacts in phase-retrieved projection images, which are then propagated to the reconstructed 3D sample representation. The problem intensifies in nano-holotomography with focusing optics, which, due to various imperfections creates high-frequency components in the probe function. Here, we present a new iterative reconstruction scheme for holotomography, simultaneously retrieving the complex-valued probe function. Implemented on GPUs, this algorithm results in 3D reconstruction resolving twice thinner layers in a 3D ALD standard sample measured using nano-holotomography.

Nikitin, Viktor↗

Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

25 ENERGY STORAGE↗

Influences of Alkali Metal Cation Interactions on N2 Coordination to Iron(I) Beta-Diketiminate Complexes in Electrolyte Solutions

N2 functionalization reactions often use stable, isolable N2-bound complexes and low temperatures or highly activated reagents. However, little work has focused on systems where N2 binds weakly, and the N2 binding equilibrium can be modulated. Here, we describe analysis of surprising trends in alkali metal cation solvation on the formation of an anionic iron(I) beta-diketiminate complex and the subsequent N2 binding equilibrium. Variable temperature UV-vis spectroscopy shows that increased ionic strength in the coordinating solvent tetrahydrofuran promotes N2 coordination. Additionally, less solvated alkali metal cations in noncoordinating 2-methyltetrahydrofuran (MeTHF) stabilize N2 coordination, likely through the formation of contact ion pairs in solution that have enhanced N2 binding. Ionic strength has little effect on the energetics of N2 coordination to these proposed contact ion pairs in MeTHF. When the electrochemical analysis is done at –78 °C, there is an irreversible reduction of iron(II) and an anodically shifted oxidation, which is attributed to the formation of the spectroscopically observed N2 complex. Finally, bulk electrolysis is used to verify the electrochemical formation of the N2-bound anionic iron(I) complex. These studies demonstrate a new strategy for promoting N2 coordination by changing solution properties, which is relevant to homogeneous electrochemical N2 reduction methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unitarity of quantum tunneling decay for an analytical exact non-Hermitian resonant-state approach

Highlights: • Foundations of quantum mechanics • Quantum decay • Non-Hermitian Hamiltonian • Unitarity • Resonant state By using an analytical exact non-Hermitian formalism for quantum tunneling decay that involves the expansion of the decaying wave function as a linear combination of resonant states and transient functions associated with the complex poles of the outgoing Green’s function to the problem, it is shown that the integrated decaying probability density in the whole space satisfies unitarity at each value of time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

On-shell recursion and holomorphic HQET for heavy quark hadronic resonances

We develop a new theoretical framework for the treatment of heavy quark (HQ) resonances within heavy quark effective theory (HQET). This framework uses on-shell recursion techniques to express the resonant amplitude as a product of on-shell subamplitudes, which allows one to employ a form-factor representation of the hadronic matrix elements and to obtain an HQ expansion, but at the price of introducing complex momenta. We construct a generalized “holomorphic HQET” onto which such complex-momentum matrix elements can be matched, and we show that PT symmetry ensures the Isgur-Wise functions (and the perturbative corrections) become holomorphic functions of the complex recoil parameter with real coefficients. They are thus an analytic continuation of the standard HQET description. This framework admits a HQ hadron (strong decay) width expansion. At second order, we show it is compatible with data for the B12∗$$ {B}_{1(2)}^{\left(\ast \right)} $$ and D12∗$$ {D}_{1(2)}^{\left(\ast \right)} $$ HQ doublets. Taking the B¯→D1∗1−→Dπlν$$ \overline{B}\to \left({D}_1^{\ast}\left({1}^{-}\right)\to D\pi \right) l u $$ system as an example, we compute the holomorphic HQET expansion to first order, as well as the complex-momentum on-shell subamplitudes. A toy numerical study of the resulting differential rates demonstrates that this framework generates HQ resonance lineshapes with large tails, resembling those seen in data.

Manzari, Claudio Andrea↗

FunDiff: diffusion models over function spaces for physics-informed generative modeling

Recent advances in generative modeling-particularly diffusion models and flow matching-have been widely used for synthesizing discrete data such as images and videos. However, adapting these models to physical applications remains challenging, as the quantities of interest are continuous functions governed by complex physical laws. To address this, we introduce FunDiff, an efficient and robust framework for generative modeling in function spaces. FunDiff combines a latent diffusion process with a function autoencoder architecture to handle input functions with varying discretizations, generates continuous functions that can be evaluated at arbitrary locations, and seamlessly incorporate physical priors. These priors are enforced through architectural constraints or physics-informed loss functions, ensuring that generated samples satisfy fundamental physical laws. We theoretically establish minimax optimality guarantees for density estimation in function spaces, demonstrating that diffusion-based estimators achieve optimal convergence rates under suitable regularity conditions. We further demonstrate the practical effectiveness of FunDiff across diverse applications in fluid dynamics and solid mechanics. Empirical results indicate that our method can generate physically consistent samples with high fidelity to the target distribution, and exhibit robustness to noisy and low-resolution data.

Wang, Sifan [Yale University, New Haven, CT (Unite↗

Cryo-EM captures the coordination of asymmetric electron transfer through a di-copper site in DPOR

Enzymes that catalyze long-range electron transfer (ET) reactions often function as higher order complexes that possess two structurally symmetrical halves. The functional advantages for such an architecture remain a mystery. Using cryoelectron microscopy we capture snapshots of the nitrogenase-like dark-operative protochlorophyllide oxidoreductase (DPOR) during substrate binding and turnover. DPOR catalyzes reduction of the C17 = C18 double bond in protochlorophyllide during the dark chlorophyll biosynthetic pathway. DPOR is composed of electron donor (L-protein) and acceptor (NB-protein) component proteins that transiently form a complex in the presence of ATP to facilitate ET. NB-protein is an α 2 β 2 heterotetramer with two structurally identical halves. However, our structures reveal that NB-protein becomes functionally asymmetric upon substrate binding. Asymmetry results in allosteric inhibition of L-protein engagement and ET in one half. Residues that form a conduit for ET are aligned in one half while misaligned in the other. An ATP hydrolysis-coupled conformational switch is triggered once ET is accomplished in one half. These structural changes are then relayed to the other half through a di-nuclear copper center at the tetrameric interface of the NB-protein and leads to activation of ET and substrate reduction. These findings provide a mechanistic blueprint for regulation of long-range electron transfer reactions.

Computational biophysics↗

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗

Improved Operational Stability of Blue Phosphorescent OLEDs by Functionalizing Phenyl‐Carbene Groups of Tetradentate Pt(II) Complexes

Abstract Stable and efficient deep‐blue organic light‐emitting diodes (OLEDs) are in high demand for display and lighting applications but are rarely reported due to their poor operational lifetimes. Herein, the study designs and synthesizes two novel N ‐heterocyclic carbene (NHC)‐based tetradentate Pt(II) complexes PtON5‐dtb and PtON5N‐dtb, and thoroughly investigate their electrochemical and photophysical properties. Functionalization of the NHC moieties can increase the metal‐to‐ligand charge transfer ( 1/3 MLCT) characters in their lowest triplet excited‐states, resulting in significantly shortened photoluminescent lifetimes and remarkably improved device performance. A deep blue OLED employing PtON5N‐dtb as an emitter exhibits a narrow spectral bandwidth with a full‐width at half maximum (FWHM) of 30 nm and a CIE y value of 0.17 and demonstrates a maximum external quantum efficiency (EQE) of 20.4% with a small efficiency roll‐off, which maintains a high EQE of 18.5% at 1000 cd m −2 . Moreover, the deep blue OLED also realizes a long‐measured operational lifetime LT 90 (time to 90% of the initial luminance) of 71 hours with an initial brightness of 1134 cd m −2 , corresponding to an estimated device lifetime LT 90 of 85 h at 1000 cd m −2 . This represented an eightfold lifetime improvement for PtON5N‐dtb‐based deep blue OLED compared to PtON7‐dtb in the same device setting.

Li, Guijie↗

Wavelength modulation laser-induced fluorescence for plasma characterization

Laser-Induced Fluorescence (LIF) spectroscopy is an essential tool for probing ion and atom velocity distribution functions (VDFs) in complex plasmas. VDFs carry information about the kinetic properties of species that is critical for plasma characterization. Accurate interpretation of these functions is challenging due to factors such as multicomponent distributions, broadening effects, and background emissions. Our research investigates the use of Wavelength Modulation (WM) LIF to enhance the sensitivity of VDF measurements. Unlike standard Amplitude Modulation (AM) methods, WM–LIF measures the derivative of the LIF signal. This approach makes variations in VDF shape more pronounced. VDF measurements with WM–LIF were investigated with both numerical modeling and experimental measurements. The developed model enables the generation of both WM and AM signals, facilitating comparative analysis of fitting outcomes. Experiments were conducted in a weakly collisional argon plasma with magnetized electrons and non-magnetized ions. Measurements of the argon ion VDFs employed a narrow-band tunable diode laser, which scanned the 4p 4 D 7/2 –3d 4 F 9/2 transition centered at 664.553 nm in vacuum. A lock-in amplifier detected the second harmonic WM signal, which was generated by modulating the laser wavelength with an externally controlled piezo-driven mirror of the diode laser. Finally, our findings indicate that the WM–LIF signal is more sensitive to fitting parameters, allowing for better identification of VDF parameters such as the number of distribution components, their temperatures, and velocities. In addition, WM–LIF can serve as an independent method to verify AM measurements and is particularly beneficial in environments with substantial light noise or background emissions, such as those involving thermionic cathodes and reflective surfaces.

47 OTHER INSTRUMENTATION↗