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At least 829 records · Page 46

Maximizing machine learning interatomic potential transferability for the discovery of the novel stellated octadecagon Bi18-Pt24 cage structure

Achieving true transferability remains the central challenge for Machine Learning Interatomic Potentials (ML-IAPs) in modeling complex bimetallic nanoclusters across their vast potential energy surfaces. We systematically investigate data selection strategies to optimize the Chebyshev Interaction Model for Efficient Simulation (ChIMES) potential for the Bi-Pt nanoclusters by comparing three innovative sampling methods: Principal Component Analysis (PCA)/k-means (structural diversity), t-distributedStochasticNeighborEmbedding (t-SNE)/k-means (force-space diversity), and hierarchical clustering. Quantitatively, the PCA/k-means strategy proved most effective for global accuracy, yielding the lowest force errors and achieving energy root mean square errors (RMSE) values competitive with Density Functional Theory (DFT), demonstrating excellent accuracy (19.16meV/atom). Structural validation on 34 unique DFT-optimized isomers further confirmed the potential’s high fidelity, with the best model PCA/k-means reproducing structures with an average root mean square deviation (RMSD) of 0.10 Å. However, the t-SNE methods, by maximizing diversity in the force space, demonstrated superior extrapolative power, leading to the more precise prediction of a novel stellated octadecagon Bi18⁢Pt24 cage structure, demonstrating the potential for exploring previously unseen morphologies. Our results establish a clear methodology for strategic data sampling that successfully maximizes ML-IAP transferability, providing an accurate and computationally efficient tool that accelerates the theoretical discovery of complex bimetallic architectures.

Vangheluwe, Raphaël [Université Paris-Saclay, CNRS↗

Projector-Free Capped-Fragment Scheme within Density Functional Embedding Theory for Covalent and Ionic Compounds

Quantum-mechanics-(QM)-based simulations now routinely aid in understanding and even discovering new chemistries involving molecules and materials exhibiting desired functionalities. Ab initio correlated wavefunction (CW) theories systematically improve QM methods, with many exhibiting high accuracy. However, execution of CW methods requires expensive computations that typically scale poorly with system size. Divide-and-conquer approaches partition large systems into smaller fragments; a lower level of theory treats fragment interactions while a preferred higher level of theory describes the important fragment. These methods offer ways to incorporate CWs into chemical simulations of large systems, e.g., biomolecules, surfaces, large inorganic clusters, bulk crystals, etc. Here we propose a partitioning protocol that utilizes capping atoms to saturate severed covalent bonds at fragment interfaces and density functional embedding theory (DFET) to describe fragment interactions. The capping groups in each fragment provide an ad-hoc potential that approximates the effects of the environment. An embedding potential optimized via DFET then serves as an augmentation of the capping group to simulate the effects of the environment. We concurrently use an auxiliary fragment (a separate system comprised of only the combined capping groups) to account for, and thereby correct, the electron density contributions of all the capping groups added to all of the fragments. This method depends only on the capped-subsystem and auxiliary-fragment electron densities, forgoing, as with the original DFET developed for metallic systems, orbital-based projector approaches that determine a nonlocal action of the embedding potential onto the fragment electrons. By using an auxiliary fragment, the method maintains a purely electron-density-dependent embedding potential, substantially lessening the cost and leading to simpler implementation. In this work, we demonstrate the utility of our capped-DFET and ensuing capped embedded CW method in two contrasting systems, namely, an organic molecule and an ionic metal oxide cluster.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bridging reaction theory and nuclear structure in $π^±-$ 48 Ca scattering

Here, we extend the pion-nucleus multiple-scattering framework to include detailed second-order rescattering dynamics for nuclei with nonzero isospin. To account for intermediate charge-exchange and nucleon spin-flip effects, we develop a scattering potential that depends on the one- and two-body densities of the target nucleus. We compute one-body densities from coupled-cluster theory and two-body densities within the Hartree-Fock approximation. To estimate theoretical uncertainties, we employ modern nuclear Hamiltonians derived from chiral effective field theory. While the sensitivity to nuclear structure details is mild, second-order corrections are found to be sizable and essential for accurately reproducing differential cross sections measured in 𝜋 ± − 48 Ca elastic scattering within the Δ⁡(1232)-resonance region.

cluster models↗

All-electron, density-functional-based method for angle-resolved tunneling ionization in the adiabatic regime

Here we develop and test a method that integrates many-electron weak-field asymptotic theory (ME-WFAT) [O. I. Tolstikhin, L. B. Madsen, and T. Morishita, Phys. Rev. A 89, 013421 (2014)] in the integral representation (IR) into the density-functional-theory (DFT) framework. In particular, we present modifications of the integral formula in the IR ME-WFAT to incorporate the potential terms unique to DFT. By solving an adiabatic rate equation for the angle-resolved ionization yield in our DFT-based ME-WFAT method, we show that the results are in excellent agreement with those of real-time time-dependent density-functional-theory (TDDFT) simulations for NO, OCS, C⁢H 3 ⁢Br, and C⁢H 3 ⁢Cl interacting with one- and two-color laser fields with a fundamental wavelength of 800 nm. This agreement is significant because the WFAT calculations take only a small fraction of the time of full TDDFT calculations. These results suggest that in the wavelength region commonly used in strong-field experiments (800 nm and longer), our DFT-based WFAT treatment can be used to rapidly screen for the ionization properties of a large number of molecules as a function of alignment or orientation between the molecule and the strong field.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Improved description of light nuclei through chiral effective field theory at leading order

Here, we propose an arrangement of the most commonly invoked version of the two-nucleon chiral potential such that the low-lying amplitude zero of the 1 S 0 partial wave is captured at leading order of the effective expansion. Adopting other partial waves from the LENPIC interaction, we show how this modification yields an improved description of ground-state energies and point-proton radii of the 3 H, 4 He, and 6 He nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Circumnavigating collinear superspace

In this paper, we extend the collinear superspace formalism to include the full range of N = 1 supersymmetric interactions. Building on the effective field theory rules developed in a companion paper — Navigating Collinear Superspace — we construct collinear superspace Lagrangians for theories with non-trivial F- and D-term auxiliary fields. For (massless) Wess-Zumino models, the key ingredient is a novel type of Grassmann-valued supermultiplet whose lowest component is a (non-propagating) fermionic degree of freedom. For gauge theories coupled to charged chiral matter, the key ingredient is a novel type of vector superfield whose lowest component is a non-propagating gauge potential. This unique vector superfield is used to construct a gauge-covariant derivative; while such an object does not appear in the standard full superspace formalism, it is crucial for modeling gauge interactions when the theory is expres sed on a collinear slice. This brings us full circle, by showing that all types of N = 1 theories in four dimensions can beconstructed in collinear superspace from purely infrared considerations. We speculate that supersymmetric theories with N > 1 could also be implemented using similar collinear superspace constructions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Generalized models for inflationary preheating: Oscillations and symmetries

The paradigm of the inflationary universe provides a possible explanation for several observed cosmological properties. In order for such solutions to be successful, the universe must convert the energy stored in the inflaton potential into standard model particles through a process known as reheating. In this paper, we reconsider the reheating process for the case where the inflaton potential respects an approximate (but spontaneously broken) conformal symmetry during the reheating epoch. After reviewing the Effective Field Theory of Reheating, we present solutions for the nonlinear oscillations of the inflaton field, derive the corresponding Hill’s equation for the coupled reheating field, and determine the stability diagram for parametric resonance. For this class of models —the simplest realization being a scalar field with a quartic term—the expansion of the universe drives the coupled field toward a more unstable part of parameter space, in contrast to the standard case. We also generalize this class of models to include quadratic breaking terms in the potential during the reheating epoch and address the process of stability in that universality class of models.

Barrowes, Leia [University of Michigan, Ann Arbor]↗

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

SMEFT probes in future precision DIS experiments

We analyze the potential of future high-energy deep-inelastic scattering (DIS) experiments to probe new physics within the framework of the Standard Model effective field theory (SMEFT). We perform a detailed study of SMEFT probes at a future Large Hadron-electron Collider (LHeC) and a Future Circular lepton-hadron Collider (FCC-eh) machine, and extend previous simulations of the potential of an electron-ion collider (EIC) to include 𝑍-boson vertex corrections. Precision 𝑍-pole constraints on vertex corrections suffer from numerous degeneracies in the Wilson-coefficient parameter space. We find that both the LHeC and the FCC-eh can help remove these degeneracies present in the existing global fits of precision 𝑍-pole observables and LHC data. The FCC-eh and LHeC will in many cases improve upon the existing precision electroweak bounds on the SMEFT parameter space. This highlights the important role of precision DIS measurements for new physics studies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Voltage-Dependent Photoluminescence of Carbon Dots

Carbon dots are fluorescent carbon-based nanoparticles with great potential in bioimaging because they offer multiple imaging windows owing to their excitation dependent emission features. A recent theory study shows that emission of graphene quantum dots responds to external elec. field due to Stark effect. Inspired by this work, we have demonstrated here the first exptl. study of the Stark effect of fluorescent carbon dots synthesized via a soft-template method. The carbon dots exhibit excitation-dependent emission covering blue to orange emission range. After being encapsulated in artificial lipid bilayers, the carbon dots show voltage-sensitivity of fluorescence. The fluorescence intensity change per mV is comparable with that of com. membrane potential sensing dyes. Our results demonstrate the great potential of carbon dots in membrane voltage sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Superconductivity at carrier density 10 17 cm – 3 in quasi-one-dimensional Li 0.9 Mo 6 O 17

Superconductivity is a fascinating phenomenon that involves an attractive interaction by which electrons are paired and can move without electrical resistance below a critical temperature T c . A paradigm for understanding superconductive pairing, the successful “BCS” theory, developed more than 65 years ago, is challenged by certain classes of materials for which parameters (e.g. the value of T c , the density of electrons, etc.) fall outside the range for which BCS theory is applicable. The study of such materials is important because new physics may be revealed and because superconductivity has many potential applications in sensing and electronics. Superconductivity at very low carrier density is a rare and fascinating phenomenon that is of considerable importance and interest in condensed matter physics. The conditions of high density of states and effective screening of Coulomb repulsion, both key ingredients of stable Cooper pairing in the BCS theory, may not be met at low carrier density. Thus, such systems may also harbor unconventional electron pairing (e.g. non-phononic) or pairing without phase coherence as a precursor to Bose-Einstein condensation. An intriguing route toward extreme low-density (and possibly unconventional) superconductivity may be found in quasi-one-dimensional metals for which density-wave instabilities compete for the ground state and can lead to gapping of substantial portions of the Fermi surface (FS), leaving a residual (reconstructed) FS comprising a very small carrier density. Our work highlights a novel material in this unusual category: Li 0.9 Mo 6 O 17 (T c =2 K) (also known as "lithium purple bronze" or "LiPB"). We present both electrical and thermoelectric magnetotransport measurements that reveal superconductivity to occur at carrier density 2 x10 17 cm -3 , among the lowest known for any superconductor, and four orders of magnitude lower than is expected from its chemical valence and band structure. With its exceptionally large ratio of superconducting to Fermi temperature, T c /TF ≳ 0.1, LiPB is properly placed at the top of a very small group of superconductors (including cuprates, heavy-fermion and Fe-based superconductors) for which this ratio falls in the BCS-BEC crossover regime and for which pairing is believed to be spin mediated.

36 MATERIALS SCIENCE↗

Nonlinear Lifshitz photon theory in condensed matter systems

We present an interacting theory of a U(1) gauge boson with a quadratic dispersion relation, which we call the "nonlinear Lifshitz photon theory.'' The Lifshitz photon is a three-dimensional generalization of the Tkachenko mode in rotating superfluids. Starting from the Wigner crystal of charged particles coupled to a dynamical U(1) gauge field, after integrating out gapped degrees of freedom, we arrive at the Lagrangian for the nonlinear Lifshitz photon. The symmetries of the theory include a global U(1) 1-form symmetry and nonlinearly realized "magnetic" translation and rotation symmetries. The interaction terms in the theory lead to the decay of the Lifshitz photon, the rate of which we estimate. We show that the Wilson loop, which plays the role of the order parameter of the spontaneous breaking of the 1-form global symmetry, deviates from the perimeter law by an additional logarithmic factor. Here, we explore potential connections to other condensed matter systems, with a particular focus on quantum spin ice and ferromagnets. Finally, we generalize our theory to higher dimensions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Local chiral EFT potentials in nuclei and neutron matter: results and issues

In recent years, the combination of advanced quantum Monte Carlo (QMC) methods and local interactions derived from chiral effective field theory (EFT) has been shown to provide a versatile and systematic approach to nuclear systems. Calculations at next-to-next-to-leading order in chiral EFT have lead to fascinating results for nuclei and nucleonic matter. On the one hand, ground-state properties of nuclei are well reproduced up to A $≤$ 16, even though these potentials have been fit to nucleon-nucleon scattering and few-body observables only. On the other hand, a reasonable description of neutron-matter properties emerges. While regulator functions applied to two- and three-nucleon forces are a necessary ingredient in these many-body calculations, the use of local regulators leads to a substantial residual regulator and cutoff dependence that increases current theoretical uncertainties. In this contribution, we review local chiral interactions, their applications, and QMC results for nuclei and neutron matter. In addition, we address regulator issues for such potentials and present a possible path forward.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

MOF-Transformed In 2 O 3-x @C Nanocorn Electrocatalyst for Efficient CO 2 Reduction to HCOOH

For electrochemical CO 2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (J HCOOH ) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In 2 O 3-x @C nanocatalyst, wherein In 2 O 3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm –2 J HCOOH at a low potential of – 0.4 V versus RHE. At the current density of 100 mA cm –2 , the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In 2 O 3-x has exposed more In 3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In 3+ as the active site and the key intermediate of HCOO* during the process of CO 2 reduction to HCOOH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanisms of Al3+ dimerization in alkaline solutions

The molecular speciation of aluminum (Al3+) in alkaline solutions is fundamental to its precipitation chemistry within a number of industrial applications that include ore renement and industrial processing of Al wastes. Under these conditions, Al3+ is predominantly Al(OH) {4 , while at high [Al] dimeric species also known to form. To date, the mechanism of dimer formation remains unclear and it is likely infuenced by complex ion ion interactions. In the present work, we investigate the role of ion pairing and a suite of potential dimerization pathways using a three-pronged approach that consists of density functional theory-based molecular dynamics (DFTMD), static DFT calculations (sDFT) and semi-empirical density functional tight binding molecular dynamics (SEMD). Specic cation eects imparted by the background electrolyte cations Na+, Li+ and K+ have been examined. Our simulations predict that when the Al species are ion paired with either cation the formation of the oxo-bridged Al2O(OH) 2{6 is favored with respect to the dihydroxo-bridged Al2(OH) 2{8 , in agreement with previousspectroscopic work. The formation of both dimers rst proceeds by bridging of two monomeric units via one hydroxo ligand, leading to a labile Al2(OH) 2{8 isomer. The eect of contact ion pairing of Li+ and K+ on the dimerization energetics is distinctly more favorable than that of Na+, which may have an impact on further ligomerization.

Pouvreau, Maxime↗

Harmonic Infrared and Raman Spectra in Molecular Environments Using the Polarizable Embedding Model

We present a fully analytic approach to calculate infrared (IR) and Raman spectra of molecules embedded in complex molecular environments modeled using the fragment-based polarizable embedding (PE) model. We provide the theory for the calculation of analytic second-order geometric derivatives of molecular energies and first-order geometric derivatives of electric dipole moments and dipole–dipole polarizabilities within the PE model. The derivatives are implemented using a general open-ended response theory framework, thus allowing for an extension to higher-order derivatives. The embedding-potential parameters used to describe the environment in the PE model are derived through first-principles calculations, thus allowing a wide variety of systems to be modeled, including solvents, proteins, and other large and complex molecular environments. Here, we present proof-of-principle calculations of IR and Raman spectra of acetone in different solvents. This work is an important step toward calculating accurate vibrational spectra of molecules embedded in realistic environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving Rare-Earth Mineral Separation with Insights from Molecular Recognition: Functionalized Hydroxamic Acid Adsorption onto Bastnäsite and Calcite

Enhancing the separation of rare-earth elements (REEs) from gangue materials in mined ores requires an understanding of the fundamental interactions driving the adsorption of collector ligands onto mineral interfaces. In this work, we examine five functionalized hydroxamic acid ligands as potential collectors for the REE-containing bastnäsite mineral in froth flotation using density functional theory calculations and a suite of surface-sensitive analytical spectroscopies. These include vibrational sum frequency generation, attenuated total reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopies. Differences in the chemical makeup of these ligands on well-defined bastnäsite and calcite surfaces allow for a systematic relationship connecting the structure to adsorption activity to be framed in the context of interfacial molecular recognition. Here we show how the intramolecular hydrogen bonding of adsorbed ligands requires the inclusion of explicit water solvent molecules to correctly map energetic and structural trends measured by experiments. We anticipate that the results and insights from this work will motivate and inform the design of improved flotation collectors for REE ores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Selective Oxygen Reduction to Hydrogen Peroxide on a Carbon-Supported Single-Atom Pd Electrocatalyst

Selective electrochemical two-electron oxygen reduction is a promising route for renewable and on-site H 2 O 2 generation as an alternative to the anthraquinone process. In this study, we report a high-performance nitrogen-coordinated single-atom Pd electrocatalyst, which is derived from Pd-doped zeolitic imidazolate frameworks (ZIFs) through one-step thermolysis. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with X-ray absorption spectroscopy verifies atomically dispersed Pd atoms on nitrogen-doped carbon (Pd-NC). The single-atom Pd-NC catalyst exhibits excellent electrocatalytic performance for two-electron oxygen reduction to H 2 O 2 , which shows ~95% selectivity toward H 2 O 2 and an unprecedented onset potential of ~0.8 V versus revisable hydrogen electrode (RHE) in 0.1 M KOH. Density functional theory (DFT) calculations demonstrate that the Pd-N 4 catalytic sites thermodynamically prefer *–O bond breaking to O–O bond breaking, corresponding to a high selectivity for H 2 O 2 production. This work provides a deep insight into the understanding of the catalytic process and design of high-performance 2e– ORR catalysts.

36 MATERIALS SCIENCE↗