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Particle Theory and Cosmology

This project covered theoretical studies in particle physics, particle astrophysics and cosmology, aiming to bridge theoretical models with observable phenomena. The central focus was on exploring innovative mechanisms that could simultaneously address several outstanding puzzles in these areas, including the nature of dark matter, the muon g-2 anomaly, the existence of topologically stable monopoles, the generation of observable gravitational waves from early universe phenomena and high energy cosmic rays. One of the major achievements of this project was the development of models that predict new physics accessible through current and forthcoming experimental setups, both in particle colliders and astrophysical observations. These models have been instrumental in proposing verifiable predictions concerning supersymmetric extensions, the dynamics of cosmic strings and monopoles, and the intricate processes underpinning baryogenesis and reheating post-inflation. In tackling the dark matter conundrum, the project proposed several candidates within extended frameworks, such as light Z' models, pseudo-Goldstone dark matter, and scenarios integrating dark matter with inflationary cosmology. Each model outlined pathways for detection through direct, indirect, and collider search strategies, marking significant strides in the hunt for dark matter. Another cornerstone of the project was the in-depth analysis of inflationary models compliant with the Trans-Planckian Censorship Conjecture, highlighting the compatibility of axion dark matter within such frameworks. This not only provided a coherent picture of early universe cosmology but also delineated clear experimental signatures. The exploration of grand unified theories yielded insights into the potential discovery of monopoles and novel particle configurations at energy scales accessible to current and future colliders. This endeavor expanded the predictive power of these theories, particularly in the context of proton decay and the properties of Higgs-portal dark matter. Throughout the project, significant emphasis was placed on ensuring the theoretical developments were grounded in experimental testability. This led to a series of publications across prestigious journals, each contributing to the vibrant discourse at the intersection of particle physics and cosmology. In summary, this project has elucidated pathways beyond the Standard Model that are ripe for exploration through both ongoing and upcoming experimental efforts. The comprehensive approach adopted herein not only enhances our understanding of the fundamental forces and constituents of the universe but also propels the field towards new frontiers in high-energy physics and cosmology.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Thermal Conductivity of a Novel Salt-Hydrogel Complex as a Phase Change Material for Building Thermal Management

Use of electricity for space heating, ventilation and air conditioning in buildings may be better managed through temporary energy storage. Compared with electrochemical storage, the levelized cost of thermal energy storage systems can be lower depending on geographical location and thermophysical properties [1]. In any phase change material (PCM), the rate of absorption and release of thermal energy increases with higher thermal conductivity [2]. However, leading PCMs like paraffin waxes have thermal conductivities on the order of 0.1 W/mK. Glauber’s salt, a salt hydrate, possesses a relatively high thermal conductivity but suffers from supercooling and phase segregation. Research has shown that polymer-based composites with salt hydrates can prevent phase segregation and limit supercooling over hundreds of cycles [3] though the thermal conductivity of the composite may be reduced leading to low energy storage rates. Here, we report thermal conductivity measurements on polymer hydrogels which are stable in solutions of Glauber’s salt. To measure thermal conductivity of soft gels, we use a 3-omega method [4] where heat flows bidirectionally through a substrate below and through a gel placed on top. This suits measurements of both gels and liquids unlike transient plane heat source or transient hot wire methods. We report measurements of thermal conductivity of salt-hydrogel complexes as a function of temperature, cross-linking and salt concentration. In addition, we present modeling of thermal conductivity of sodium sulfate solutions with available theories. We finally employ polarized optical microscopy to observe inside the transparent hydrogel networks, showing that precipitating crystals may influence thermal conductivity measurements for high salt concentrations. Our thermal conductivity results combined with enthalpy of phase change, mass density and specific heat are essential to accurately design thermal storage systems for energy-efficient buildings.

composite, thermal conductivity↗

On Proton Defects and the Phase Transformation of NiO 2

One approach to high-capacity Li-ion battery cathodes is to increase the Ni content. Unfortunately, Ni-rich materials undergo a phase transition and volume collapse at a high state of charge (SOC), which degrades battery performance. At a high SOC, NiO 2 undergoes a phase transition from the O 3 to the O 1 phase. The O 1 phase appears to be more thermodynamically stable than the O 3 phase. However, density functional theory (DFT) often predicts higher stability for O 3 , depending on the DFT approximation. The energy difference between the O 1 and O 3 phases is on the order of 10 meV/atom. Furthermore, we find that proton defects are more stable in the O 1 phase than in the O 3 phase by about 90 meV per proton. Defects in NiO 2 energetically favor the O 3 -O 1 phase transition observed in a high SOC in Li $x$ NiO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of high invariant-mass Drell-Yan forward-backward asymmetry measurements on SMEFT fits

We study the impact of LHC forward-backward asymmetry (AFB) measurements at high invariant mass in the Drell-Yan process on probes of semileptonic four-fermion operators in the Standard Model effective field theory (SMEFT). In particular, we study whether AFB measurements can resolve degeneracies in the Wilson coefficient parameter space that appear when considering invariant-mass and rapidity measurements alone. We perform detailed fits of the available high-energy and high-luminosity ATLAS and CMS data for both invariant-mass distributions and AFB. While each type of measurement separately exhibits degeneracies, combining them removes these blind spots in some cases. In other situations, it does not, highlighting the importance of incorporating future datasets from other experiments to fully explore this sector of the SMEFT. We investigate the impact of contributions quadratic in the Wilson coefficients on the description of Drell-Yan data and discuss when such terms are important in joint fits of the AFB and invariant-mass data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Convergent Protocols for Computing Protein–Ligand Interaction Energies Using Fragment-Based Quantum Chemistry

Fragment-based quantum chemistry methods offer a way to sidestep the steep nonlinear scaling of electronic structure calculations so that large molecular systems can be investigated using high-level methods. Here, we use fragmentation to compute protein–ligand interaction energies in systems with several thousand atoms, using a new software platform for managing fragment-based calculations that implements a screened many-body expansion. Convergence tests using a minimal-basis semiempirical method (HF-3c) indicate that two-body calculations, with single-residue fragments and simple hydrogen caps, are sufficient to reproduce interaction energies obtained using conventional supramolecular electronic structure calculations, to within 1 kcal/mol at about 1% of the computational cost. We also demonstrate that the HF-3c results are illustrative of trends obtained with density functional theory in basis sets up to augmented quadruple-ζ quality. Strategic deployment of fragmentation facilitates the use of converged biomolecular model systems alongside high-quality electronic structure methods and basis sets, bringing ab initio quantum chemistry to systems of hitherto unimaginable size. This will be useful for generation of high-quality training data for machine learning applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the Li Diffusion Mechanism in Si/C Composite Anodes for Lithium-Ion Batteries

Recently, Si/C composite materials have attracted enormous research interest as the most promising candidates for the anodes of next-generation lithium-ion batteries, owing to their high energy density and mechanical buffering property. However, the fundamental mechanism of Li diffusion behavior in various Si/C composite materials remains unclear, with our understanding limited by experimental techniques and continuum modeling methodologies. Herein, the atomic behavior of Li diffusion in the Si/C composite material is studied within the framework of density functional theory. Two representative structural mixing formats, that is, simple mixture mode and core-shell mode, are modeled and compared. We discover that the carbon material increases Li diffusion in silicon from 7.75 x 10 -5 to 2.097 x 10 -4 cm 2 /s. The boost is about 50% more obvious in the mixture mode, while the core-shell structure shows more dependence on the atomic structures of the carbon layer. These results offer new insights into Li diffusion behavior in Si/C composites and unlock the enhancing mechanism for Li diffusion in Si/C. Furthermore, this understanding facilitates the modeling of batteries with composite anodes and will guide the corresponding structure designs for robust and high-energy-density batteries.

25 ENERGY STORAGE↗

FY2018 Fusion Theory and Simulation Milestone on Plasma Materials Interaction (PMI) (Final Report)

The interaction of the boundary plasma with the material surfaces in magnetically confined plasmas is among the most critical problems in fusion energy science. In FY2018, perform high performance computing simulations with coupled boundary plasma physics and materials surface models to predict the fuel recycling and tritium retention of the ITER divertor for D-T burning plasma conditions, accounting for erosion, re-deposition and impurity transport in the plasma boundary, and an initial evaluation of the influence of material deposition on the recycling and retention.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Density Functional Tight-Binding Models for Band Structures of Transition-Metal Alloys and Surfaces across the d -Block

First-principles electronic structure simulations are an invaluable tool for understanding chemical bonding and reactions. While machine-learning models such as interatomic potentials significantly accelerate the exploration of potential energy surfaces, electronic structure information is generally lost. Particularly in the field of heterogeneous catalysis, simulated electron band structures provide fundamental insights into catalytic reactivity. This ab initio knowledge is preserved in semiempirical methods such as density functional tight binding (DFTB), which extend the accessible computational length and time scales beyond first-principles approaches. In this paper here we present Shell-Optimized Atomic Confinement (SOAC) DFTB electronic-part-only parametrizations for bulk and surface band structures of all d-block transition metals that enable efficient predictions of electronic descriptors for large structures or high-throughput studies on complex systems outside the computational reach of density functional theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Muon Collider Forum report

A multi-TeV muon collider offers a spectacular opportunity in the direct exploration of the energy frontier. Offering a combination of unprecedented energy collisions in a comparatively clean leptonic environment, a high energy muon collider has the unique potential to provide both precision measurements and the highest energy reach in one machine that cannot be paralleled by any currently available technology. The topic generated a lot of excitement in Snowmass meetings and continues to attract a large number of supporters, including many from the early career community. In light of this very strong interest within the US particle physics community, Snowmass Energy, Theory and Accelerator Frontiers created a cross-frontier Muon Collider Forum in November of 2020. The Forum has been meeting on a monthly basis and organized several topical workshops dedicated to physics, accelerator technology, and detector R&D. Findings of the Forum are summarized in this report.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reaction

Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.

08 HYDROGEN↗

Angular fractals in thermal QFT

We show that thermal effective field theory controls the long-distance expansion of the partition function of a d-dimensional QFT, with an insertion of any finite-order spatial isometry. Consequently, the thermal partition function on a sphere displays a fractal-like structure as a function of angular twist, reminiscent of the behavior of a modular form near the real line. As an example application, we find that for CFTs, the effective free energy of even-spin minus odd-spin operators at high temperature is smaller than the usual free energy by a factor of 1/2 d . Near certain rational angles, the partition function receives subleading contributions from “Kaluza-Klein vortex defects” in the thermal EFT, which we classify. We illustrate our results with examples in free and holographic theories, and also discuss nonperturbative corrections from worldline instantons.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

BUQEYE guide to projection-based emulators in nuclear physics

The BUQEYE collaboration (Bayesian Uncertainty Quantification: Errors in Your effective field theory) presents a pedagogical introduction to projection-based, reduced-order emulators for applications in low-energy nuclear physics. The term emulator refers here to a fast surrogate model capable of reliably approximating high-fidelity models. As the general tools employed by these emulators are not yet well-known in the nuclear physics community, we discuss variational and Galerkin projection methods, emphasize the benefits of offline-online decompositions, and explore how these concepts lead to emulators for bound and scattering systems that enable fast and accurate calculations using many different model parameter sets. We also point to future extensions and applications of these emulators for nuclear physics, guided by the mature field of model (order) reduction. All examples discussed here and more are available as interactive, open-source Python code so that practitioners can readily adapt projection-based emulators for their own work.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

An Accurate Potential Energy Surface for H2O

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

Schwenke, David W.↗

Interactive multiscale modeling to bridge atomic properties and electrochemical performance in Li-CO 2 battery design

Li-CO 2 batteries are promising energy storage systems due to their high theoretical energy density and CO 2 fixation capability, relying on reversible Li 2 CO 3 /C formation during discharge/charge cycles. Here, we present a multiscale modeling framework integrating Density Functional Theory (DFT), Ab-Initio Molecular Dynamics (AIMD), classical Molecular Dynamics (MD), and Finite Element Analysis (FEA) to investigate atomic and cell-level properties. The considered Li-CO 2 battery consists of a lithium metal anode, an ionic liquid electrolyte, and a carbon cloth cathode with Sb 0.67 Bi 1.33 Te 3 catalyst. DFT and AIMD determined the electrical conductivities of Sb 0.67 Bi 1.33 Te 3 and Li 2 CO 3 using the Kubo–Greenwood formalism and studied the CO 2 reduction mechanism on the cathode catalyst. MD simulations calculated the CO 2 diffusion coefficient, Li + transference number, ionic conductivity, and Li + solvation structure. The FEA model, parameterized with atomistic simulation data, reproduced the available experimental voltage–capacity profile at 1 mA/cm 2 and revealed spatio-temporal variations in Li 2 CO 3 /C deposition, porosity, and CO 2 concentration dependence on discharge rates in the cathode. Accordingly, Li 2 CO 3 can form large and thin film deposits, leading to dispersed and local porosity changes at 0.1 mA/cm 2 and 1 mA/cm 2 , respectively. The capacity decreases exponentially from 81,570 mAh/g at 0.1 mA/cm 2 to 6200 mAh/g at 1 mA/cm 2 , due to pore clogging from excessive discharge product deposition that limits CO 2 transport to the cathode interior. Therefore, the performance of Li-CO 2 batteries can be improved by enhancing CO 2 transport, regulating Li 2 CO 3 deposition, and optimizing cathode architecture.

Battery performance↗

Effect of microphase separation on the limiting current density in hybrid organic-inorganic copolymer electrolytes

Hybrid organic-inorganic block copolymer electrolytes are of interest to enable batteries containing lithium metal anodes. The conductive block is a standard polymer electrolyte of poly(ethylene oxide) and the mechanically rigid block is an inorganic poly(acryloisobutyl polyhedral oligomeric silsesquioxane) polymer. Here, in this paper, we compare a poly(acryloisobutyl polyhedral oligomeric silsesquioxane)-b-poly(ethylene oxide)-b-poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (POSS-PEO-POSS) triblock copolymer and a poly(ethylene oxide)-b- poly(acryloisobutyl polyhedral oligomeric silsesquioxane) (PEO-POSS) diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide salt. We have experimentally measured the limiting current density in lithium symmetric cells containing hybrid organic-inorganic electrolytes at 90 °C. The cells were polarized at a large range of applied current density. The diblock copolymer electrolyte exhibited a clear plateau in cell potential at all current densities below the limiting current density. At low applied current density, the triblock copolymer electrolyte also exhibited a clear plateau in cell potential. At currents approaching the limiting current density, the triblock copolymer electrolyte exhibited an underdamped potential profile. The cell potential did not reach a plateau at current densities above the limiting current in both systems. The diblock and triblock copolymer electrolytes were fully characterized using electrochemical methods to determine the ionic conductivity, cation current fraction, salt diffusion coefficient, and open circuit voltage as a function of salt concentration. Cell potential and salt concentration as functions of position in the cell at various current densities were calculated using Newman's concentrated solution theory. The theoretical limiting current density was calculated to be the current density at which salt is depleted at the cathode. We see quantitative agreement between experimental measurements and theoretical predictions for the limiting current density in the diblock copolymer electrolyte which has an ordered structure at all salt concentrations, while the experimental limiting current density is lower than the theoretical prediction for the triblock copolymer electrolyte, which exhibits a disordered morphology at high salt concentrations.

25 ENERGY STORAGE↗

Controllable Formation of Threefold-Coordinated Oxygen in Graphene by Low-Energy Ion Implantation

The atomically precise engineering of impurities in graphene and the understanding of their structural and carrier-dependent electronic properties at the nanoscale are crucial for advancing graphene-based nanoelectronics, catalysis, and energy technologies. Here, we demonstrate controllable incorporation of the elusive 3-fold-coordinated O substitutions into graphene using low-energy O + ion implantation under ultrahigh-vacuum conditions. By combining high-resolution scanning tunneling microscopy and spectroscopy (STM/S), bond-resolved noncontact atomic force microscopy techniques, and density functional theory (DFT) calculations, we resolve both the structural and electronic properties of the O-related defects. The STM/S measurements, corroborated by DFT calculations, uncover a characteristic impurity state that is energetically pinned to the Dirac point across different charge-carrier doping regimes. Molecular dynamics simulations further reveal the distribution of implantation-induced configurations and identify the formation of 3-fold-coordinated O dopants. Furthermore, this work provides a viable route to incorporate 3-fold-coordinated O dopants and opens new opportunities for controlled defect engineering in graphene.

3-fold-coordinated oxygen↗

Interfacial Charge Transfer Pathways in Photoelectrochemical H 2 Evolution by a Single-Component Molecular Catalyst on a Conductive Metal Oxide

Dye-sensitized photoelectrosynthesis cells traditionally combine a photosensitizing dye to harvest light and a catalyst to generate chemical fuels on a semiconductor. Here, in this work, a photoactive catalyst capable of both light absorption and fuel formation, [Cp*Ir(4,4′-Y 2 -bpy)Cl][Cl] (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine, Y = CH 2 PO 3 H 2 ), is anchored to a mesoporous tin-doped indium oxide (ITO) electrode and facilitates photoelectrochemical H 2 evolution in water without the need for additional photosensitizers or sacrificial reductants. Spectroelectrochemistry indicates a single-site H 2 evolution mechanism involving charge injection to ITO, in contrast to the bimetallic mechanism observed in solution. Cyclic voltammetry and variable-potential chronoamperometry under illumination probe competing pathways via interfacial electron transfer between the Ir hydride excited state and the conductive ITO electrode. A Marcus theory framework provides reorganization energies for competing interfacial electron transfer pathways from potential-dependent quantum yield measurements. The light-driven H 2 evolution catalysis on conducting oxide proceeds with high Faradaic efficiency and current densities comparable to photoelectrodes utilizing p-type semiconductors. By uncovering the principal electron transfer pathways that govern photocatalytic efficiency, this study establishes design principles for hybrid molecular photoelectrocatalysts.

catalysts↗

Computational general relativistic force-free electrodynamics: II. Characterization of numerical diffusivity

Scientific codes are an indispensable link between theory and experiment; in (astro-)plasma physics, such numerical tools are one window into the universe’s most extreme flows of energy. The discretization of Maxwell’s equations – needed to make highly magnetized (astro)physical plasma amenable to its numerical modeling – introduces numerical diffusion. It acts as a source of dissipation independent of the system’s physical constituents. Understanding the numerical diffusion of scientific codes is the key to classifying their reliability. It gives specific limits in which the results of numerical experiments are physical. We aim at quantifying and characterizing the numerical diffusion properties of our recently developed numerical tool for the simulation of general relativistic force-free electrodynamics by calibrating and comparing it with other strategies found in the literature. Our code correctly models smooth waves of highly magnetized plasma. We evaluate the limits of general relativistic force-free electrodynamics in the context of current sheets and tearing mode instabilities. We identify that the current parallel to the magnetic field (j ∥ ), in combination with the breakdown of general relativistic force-free electrodynamics across current sheets, impairs the physical modeling of resistive instabilities. We find that at least eight numerical cells per characteristic size of interest (e.g., the wavelength in plasma waves or the transverse width of a current sheet) are needed to find consistency between resistivity of numerical and of physical origins. High-order discretization of the force-free current allows us to provide almost ideal orders of convergence for (smooth) plasma wave dynamics. The physical modeling of resistive layers requires suitable current prescriptions or a sub-grid modeling for the evolution of j ∥ .

79 ASTRONOMY AND ASTROPHYSICS↗