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At least 109 records · Page 6

The Principle of Maximum Conformality Correctly Resolves the Renormalization-Scheme-Dependence Problem

In this paper, we clarify a serious misinterpretation and consequent misuse of the Principle of Maximum Conformality (PMC), which also can serve as a mini-review of PMC. In a recently published article, P. M. Stevenson has claimed that “the PMC is ineffective and does nothing to resolve the renormalization-scheme-dependence problem”, concluding incorrectly that the success of PMC predictions is due to the PMC being a “laborious, ad hoc, and back-door” version of the Principle of Minimal Sensitivity (PMS). We show that such conclusions are incorrect, deriving from a misinterpretation of the PMC and an overestimation of the applicability of the PMS. The purpose of the PMC is to achieve precise fixed-order pQCD predictions, free from conventional renormalization schemes and scale ambiguities. We demonstrate that the PMC predictions satisfy all the self-consistency conditions of the renormalization group and standard renormalization-group invariance; the PMC predictions are thus independent of any initial choice of renormalization scheme and scale. The scheme independence of the PMC is also ensured by commensurate scale relations, which relate different observables to each other. Moreover, in the Abelian limit, the PMC dovetails into the well-known Gell-Mann–Low framework, a method universally revered for its precision in QED calculations. Due to the elimination of factorially divergent renormalon terms, the PMC series not only attains a convergence behavior far superior to that of its conventional counterparts but also deftly curtails any residual scale dependence caused by the unknown higher-order terms. This refined convergence, coupled with its robust suppression of residual uncertainties, furnishes a sound and reliable foundation for estimating the contributions from unknown higher-order terms. Anchored in the bedrock of standard renormalization-group invariance, the PMC simultaneously eradicates the factorial divergences and eliminates superfluous systematic errors, which inversely provides a good foundation for achieving high-precision pQCD predictions. Consequently, owing to its rigorous theoretical underpinnings, the PMC is eminently applicable to virtually all high-energy hadronic processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

SALSAA: a statistical approach to line shapes from an average atom

Ion-Stark line broadening is a key density diagnostic for hot dense plasmas relevant to inertial fusion and astrophysics. It is caused by interactions of a radiating ion with nearby perturbing ions, whose electric microfields lead to changes in bound-bound transition energies. Ion-Stark broadening becomes increasingly difficult to compute for complex, many-electron ions with myriad transitions. In this paper, we propose a simplified approach to ion-Stark broadening based on self-consistent ion distributions and electronic structure from an average-atom model. We find that this approach reproduces the line shape predictions of one traditional method for high-n K-shell emission lines in aluminum ions with accuracy sufficient for density diagnostics in thermal plasmas with equal ion and electron temperatures. We expect that this approach can be extended to provide a reasonable picture of ion-Stark broadening in many-electron ions, enabling rapid calculations of line profiles in complex spectra.

average-atom↗

A molecular ground electronic state with an occupied 5g spinor—The superheavy (E125)F molecule

Fully relativistic calculations, primarily at the 4-component coupled-cluster singles and doubles with perturbative triples [CCSD(T)] level of theory with the Dirac–Coulomb (DC) Hamiltonian, have been carried out for the superheavy (E125)F molecule using large Gaussian basis sets. The electronic ground state is determined to have an [Og]8s 2 5g 1 6f 3 configuration on E125 with an Ω = 6 ground state and an 8p electron largely donated to F. A Mulliken population analysis indicates that the ground state is mainly ionic with a partial charge of +0.79 on E125 and a single sigma bond involving the F 2p and E125 8p spinors. The occupied g spinor is not involved in the bonding. With the largest basis set used in this work, the (0 K) dissociation energy was calculated at the DC-CCSD(T) level of theory to be 7.02 eV. Analogous calculations were also carried out for the E125 atom, both the neutral and its cation. The lowest energy electron configuration of E125 + , [Og]$8s$$^{2}_{1/2}$$5g$$^{1}_{7/2}$$6f$$^{3}_{5/2}$ with a J = 6 ground state, was found to be similar to that in (E125)F, while the neutral E125 atom has an [Og]$8s$$^{2}_{1/2}$$5g$$^{1}_{7/2}$$6f$$^{2}_{5/2}$$7d$$^{1}_{3/2}$$8p$$^{1}_{1/2}$ ground state electron configuration with a J = 17/2 ground state. The ionization energy (IE) of E125 is reported for the first time and is calculated to be 4.70 eV at the DC-CCSD(T) level of theory. Non-relativistic calculations were also carried out on the E125 atom and the (E125)F molecule. Here, the non-relativistic ground state of the E125 atom was calculated to have a 5g 5 ground state with an IE of just 3.4 eV. The net effect of relativity on (E125)F is to stabilize its bonding.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Self-consistent interaction of linear gravitational and electromagnetic waves in non-magnetized plasma

Here, this paper explores the hybridization of linear metric perturbations with linear electromagnetic (EM) perturbations in non-magnetized plasma for a general background metric. The local wave properties are derived from first principles for inhomogeneous plasma, without assuming any symmetries of the background metric. First, we derive the effective (“oscillation-center”) Hamiltonian that governs the average dynamics of plasma particles in a prescribed quasimonochromatic wave that involves metric perturbations and EM fields simultaneously. Then, using this Hamiltonian, we derive the backreaction of plasma particles on the wave itself and obtain gauge-invariant equations that describe the resulting self-consistent gravito-electromagnetic (GEM) waves in a plasma. The transverse tensor modes of gravitational waves are found to have no interaction with the plasma and the EM modes in the geometrical-optics limit. However, for $longitudinal$ GEM modes with large values of the refraction index, the interplay between gravitational and EM interactions in plasma can have a strong effect. In particular, the dispersion relation of the Jeans mode is significantly affected by electrostatic interactions. As a spin-off, our calculation also provides an alternative resolution of the so-called Jeans swindle.

79 ASTRONOMY AND ASTROPHYSICS↗

Assessing time-dependent temperature profile predictions using reduced transport models for high performing NSTX plasmas

Time-dependent, predictive simulations were performed with the 1.5D tokamak integrated modeling code TRANSP on a large set of well-analyzed, high performing discharges from the National Spherical Torus Experiment (NSTX) in order to evaluate how well modern reduced transport models can reproduce experimentally observed temperature profiles in spherical tokamaks. Overall, it is found that simulations using the Multi-Mode Model (MMM) more consistently agree with the NSTX observations than those using the Trapped Gyro-Landau Fluid (TGLF) model, despite TGLF requiring orders of magnitude greater computational cost. When considering all examined discharges, MMM has median overpredictions of electron temperature (T e ) and ion temperature (T i ) profiles of 28% and 27%, respectively, relative to the experiment. TGLF overpredicts T e by 46%, with much larger variance than MMM, and underpredicts T i by 25%. As the ratio of kinetic to magnetic field pressure (β) is increased across NSTX discharges, TGLF predicts lower T e and significant flattening of the T i profile, conflicting with NSTX observations. When using an electrostatic version of TGLF, both T e and T i are substantially overpredicted, underscoring the importance of electromagnetic turbulence in the high β spherical tokamak regime. Additionally, calculations with neural net surrogate models for TGLF were performed outside of TRANSP with a time slice flux matching transport solver, finding better agreement with experiment than the TRANSP simulations, highlighting the impact of different transport solvers and simulation techniques. Furthermore, the reasonable agreement with experiment of temperature profiles predicted by MMM motivates a more detailed examination of the sensitivities of the TRANSP simulations with MMM to different NSTX plasma regimes in a companion paper (Lestz et al Plasma Phys. Control. Fusion 67 105030), in preparation for self-consistent, time-dependent predictive modeling of NSTX-U scenarios.

Lestz, J. B. [General Atomics, San Diego, CA (Unit↗

Charge self-consistent density functional theory plus ghost rotationally invariant slave-boson theory for correlated materials

We present a charge self-consistent density functional theory combined with the ghost rotationally invariant slave-boson (DFT+gRISB) formalism for studying correlated materials. Here, this method is applied to SrVO 3 and NiO, representing prototypical correlated metals and charge-transfer insulators. For SrVO 3 , we demonstrate that DFT+gRISB yields an accurate equilibrium volume and effective mass close to experimentally observed values. Regarding NiO, DFT+gRISB enables the simultaneous description of charge-transfer and Mott-Hubbard bands, significantly enhancing the accuracy of the original DFT+RISB approach. Furthermore, the calculated equilibrium volume and spectral function reasonably agree with experimental observations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Distinguishing homolytic vs heterolytic bond dissociation of phenylsulfonium cations with localized active space methods

Modeling chemical reactions with quantum chemical methods is challenging when the electronic structure varies significantly throughout the reaction and when electronic excited states are involved. Multireference methods, such as complete active space self-consistent field (CASSCF), can handle these multiconfigurational situations. However, even if the size of the needed active space is affordable, in many cases, the active space does not change consistently from reactant to product, causing discontinuities in the potential energy surface. The localized active space SCF (LASSCF) is a cheaper alternative to CASSCF for strongly correlated systems with weakly correlated fragments. The method is used for the first time to study a chemical reaction, namely the bond dissociation of a mono-, di-, and triphenylsulfonium cation. LASSCF calculations generate smooth potential energy scans more easily than the corresponding, more computationally expensive CASSCF calculations while predicting similar bond dissociation energies. Furthermore, our calculations suggest a homolytic bond cleavage for di- and triphenylsulfonium and a heterolytic pathway for monophenylsulfonium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First principles investigation of dopants and defect complexes in CdSe$_x$Te$_{1-x}$

Se alloying is a common approach to improve the performance of CdTe solar cells by tuning the bandgap, defect levels, and carrier density. A fundamental understanding of these improvements, specifically the effect of Se alloying on the behavior of defects and dopants in CdTe, remains unclear. Here, in this work, we present a density functional theory (DFT) study of point defect energetics in CdTe and CdSe x Te 1-x with x = 0.25, leading to a comparison of how native defects, dopants (As and Cu), impurities (Cl and O), and related defect complexes behave in CdTe vs CdSe x Te 1-x . Our calculations, performed by combining semi-local and nonlocal hybrid functionals, show a general lowering of the formation energies of native defects as well as substitutional defects formed by As and Cl upon Se addition. For successful p-type doping with As, destabilizing Cl-based defects in the CdSeTe lattice would be essential. We find evidence for some low-energy defect complexes of As, Cl, and O in CdSe 0.25 Te 0.75 . The computed defect formation energies further enable estimates of temperature-dependent defect concentrations and self-consistent Fermi levels. A comparison of defect energetics with the energies of impurity phases reveals that As, Cu, Cl, and O overwhelmingly prefer being segregated to unwanted As 2 O 5 , AsCl 3 , Cd 2 AsCl 2 , and CuO x phases rather than remain at defect sites, but such segregation is less likely to happen in CdSe 0.25 Te 0.75 than in CdTe. Overall, our work presents a list of likely defects and complexes in CdTe and Se-incorporated CdTe, paving the way to explain and mitigate limited dopant activation in experimental observations.

CdTe↗

Self-consistent modeling of tokamak edge plasma transport with lithium sources

Magnetic confinement fusion devices require effective heat and particle exhaust solutions on the divertor plates to operate sustainably, especially under reactor-relevant conditions. Liquid lithium divertors have been proposed to address two major challenges: control of excessive heat flux to plasma-facing components through vapor shielding and minimization of core plasma contamination from impurities. The National Spherical Torus Experiment-Upgrade (NSTX-U) will explore lithium as a divertor material due to its potential to meet both objectives. We present a self-consistent coupling framework between the plasma boundary transport code UEDGE and the lithium wall transport code Wall–Li to evaluate the feasibility and operational limits of lithium-based divertors. The model aims to optimize lithium sourcing levels to prevent core plasma contamination via fuel dilution while ensuring divertor protection through vapor shielding. This integrated framework, applicable to any tokamak with lithium sources, dynamically adjusts lithium sourcing based on local plasma conditions and surface temperature. The coupled model is tested using NSTX-like geometry and plasma conditions to assess its performance and reliability. Wall–Li calculates lithium fluxes from plasma-facing components, incorporating physical sputtering, thermally enhanced sputtering, and evaporation driven by surface temperature and ion flux. These fluxes are reintroduced into UEDGE as neutral lithium atoms, enabling simulation of their transport and distribution within the plasma. UEDGE computes plasma and neutral transport, surface heat flux, and iteratively feeds this information back to Wall–Li. A small time step is employed to ensure numerical stability and convergence, enabling accurate simulations over typical tokamak discharge durations. This integrated modeling approach provides a robust tool for identifying operational regimes that balance effective lithium sourcing with minimal core plasma contamination, offering critical insights for optimizing lithium-based divertor systems in current and future fusion devices.

Magnetic confinement fusion↗

Element Formation in Radiation-hydrodynamics Simulations of Kilonovae

Abstract Understanding the details of r -process nucleosynthesis in binary neutron star merger (BNSM) ejecta is key to interpreting kilonova observations and identifying the role of BNSMs in the origin of heavy elements. We present a self-consistent, two-dimensional, ray-by-ray radiation-hydrodynamic evolution of BNSM ejecta with an online nuclear network (NN) up to a timescale of days. For the first time, an initial numerical relativity ejecta profile composed of the dynamical component and spiral-wave and disk winds is evolved including detailed r -process reactions and nuclear heating effects. A simple model for the jet energy deposition is also included. Our simulation highlights that the common approach of relating in postprocessing the final nucleosynthesis yields to the initial thermodynamic profile of the ejecta can lead to inaccurate predictions. Moreover, we find that neglecting the details of the radiation-hydrodynamic evolution of the ejecta in nuclear calculations can introduce deviations of up to 1 order of magnitude in the final abundances of several elements, including very light and second r -process peak elements. The presence of a jet affects element production only in the innermost part of the polar ejecta, and it does not alter the global nucleosynthesis results. Overall, our analysis shows that employing an online NN improves the reliability of nucleosynthesis and kilonova light-curve predictions.

Magistrelli, Fabio (ORCID:0009000509767851)↗

Electronic structure and exchange interactions in altermagnetic MnGeP 2 in the quasiparticle self-consistent G W approach

The quasiparticle self-consistent 𝐺⁡𝑊 method is used to study the electronic band structure, optical dielectric function, and exchange interactions in chalcopyrite, 𝐼⁢ ‾ 4 ⁢2⁢𝑑, structure MnGeP 2 . The material is found to be an antiferromagnetic semiconductor with a lowest direct gap of 2.44 eV at the Γ point and a lower indirect gap of 1.87 eV from Γ to 𝑀. The material is an altermagnet because the two magnetic atoms of opposite spin are related by a twofold rotation operation perpendicular to the main fourfold rotation inversion axis. The spin splittings along a low symmetry line like 𝑃⁢𝑁 is sizable while at k points on the diagonal mirror planes or on the twofold symmetry axes the spin splitting is zero. The exchange interactions are calculated using a linear response approach. The antiferromagnetic exchange interaction between nearest neighbors in the primitive unit cell is dominating and found to be slightly decreasing upon carrier doping but not sufficiently to change the interaction to become ferromagnetic. The bare (noninteracting) and interacting transverse spin susceptibilities, which provide interatomic site exchange interactions after averaging over the muffin-tin spheres, are calculated from the 𝐺⁡𝑊 band structure and wave functions. From these exchange interactions, the spin wave spectra are obtained along the high symmetry lines and the Néel temperature is calculated using the mean-field and Tyablikov estimations. The dielectric function and the optical absorption spectra are calculated including excitonic effects using the Bethe Salpeter equation. The exchange interactions around Mn Ge defect sites is also studied. While we find it can generate ferromagnetic interactions with neighboring spins, we did not find direct evidence of producing an overall ferromagnetic phase. First, if Mn antisites are introduced by exchanging Mn with a nearby Ge, the interactions stay largely antiferromagnetic. Second, when we add additional Mn, in other words in Mn-rich stoichiometry, the Mn Ge antisites produce a strong ferromagnetic interaction primarily with the Mn in the same basal plane but weaker ferromagnetic interaction with adjacent plane Mn. The interactions between regular lattice Mn stay antiferromagnetic as before and thus favor keeping the antiferromagnetic order along the [001] direction. Adding Mn antisites, however, does lead to a metallic band structure.

36 MATERIALS SCIENCE↗

Towards a self-consistent model of the convective core boundary in upper main sequence stars: I. 2.5D and 3D simulations

There is strong observational evidence that the convective cores of intermediate-mass and massive main sequence stars are substantially larger than those predicted by standard stellar-evolution models. However, it is unclear what physical processes cause this phenomenon or how to predict the extent and stratification of stellar convective boundary layers. Convective penetration is a thermal-timescale process that is likely to be particularly relevant during the slow evolution on the main sequence. We use our low-Mach-number S EVEN -L EAGUE H YDRO code to study this process in 2.5D and 3D geometries. Starting with a chemically homogeneous model of a 15 M ⊙ zero-age main sequence star, we construct a series of simulations with the luminosity increased and opacity decreased by the same factor, ranging from 10 3 to 10 6 . After reaching thermal equilibrium, all of our models show a clear penetration layer; its thickness becomes statistically constant in time and it is shown to converge upon grid refinement. The penetration layer becomes nearly adiabatic with a steep transition to a radiative stratification in simulations at the lower end of our luminosity range. This structure corresponds to the adiabatic ‘step overshoot’ model often employed in stellar-evolution calculations. The simulations with the highest and lowest luminosity differ by less than a factor of two in the penetration distance. The high computational cost of 3D simulations makes our current 3D data set rather sparse. Depending on how we extrapolate the 3D data to the actual luminosity of the initial stellar model, we obtain penetration distances ranging from 0.09 to 0.44 pressure scale heights, which is broadly compatible with observations.

79 ASTRONOMY AND ASTROPHYSICS↗

Self-Consistent Theory for Structural Relaxation, Dynamic Bond Exchange Times, and the Glass Transition in Polymeric Vitrimers

Here, we formulate a statistical mechanical theory for how dynamic bond exchange influences the activated hopping-driven relaxation of Kuhn segments in dynamically cross-linked networks or vitrimers over a wide range of temperatures and cross-link densities. The key new methodological aspect is to address in a self-consistent manner the dynamic consequences of bond exchange on the Kuhn segmental alpha relaxation, and vice versa. The predicted temperature dependence of the segmental alpha time of vitrimers at high temperatures remains the same as that of permanent networks, but at lower temperatures, a significant acceleration of relaxation occurs due to bond exchanges. From a mechanistic perspective, the vitrimer local cage barrier is very weakly affected by bond exchange, while the collective elastic barrier contribution decreases significantly in the deeply supercooled regime. The vitrimer glass transition temperature is predicted to grow linearly with the square root of the cross-link density, as previously found for permanent networks. Material-specific chemical effects such as cross-linker size relative to that of the normal Kuhn segment or special attraction of a cross-linker with polymers are crudely considered based on model calculations. The theory is quantitatively applied to recent experiments on dry ethylene vitrimers. Good agreements are found including that the bond exchange time follows an Arrhenius law at high enough temperatures but upward non-Arrhenius deviations emerge in the deeply supercooled regime, and a collapsed master curve of the segment alpha time exists over a wide range of cross-link densities and temperatures. Possible extensions to treat dynamic heterogeneity effects and penetrant transport in vitrimers are briefly discussed.

chemical calculations↗

Exploring the effect of ELM and code-coupling frequencies on plasma and material modeling of dynamic recycling in divertors

Abstract Integrated modeling of plasma-surface interactions provides a comprehensive and self-consistent description of the system, moving the field closer to developing predictive and design capabilities for plasma facing components. One such workflow, including descriptions for the scrape-off-layer plasma, ion-surface interactions and the sub-surface evolution, was previously used to address steady-state scenarios and has recently been extended to incorporate time-dependence and two-way information flow. The new model can address dynamic recycling in transient scenarios, such as the application presented in this paper: the evolution of W samples pre-damaged by helium and exposed to ELMy H-mode plasmas in the DIII-D DiMES. A first set of simulations explored the effect of ELM frequency. This study was discussed in detail in this conference’s proceedings and is summarized here. The 2nd set of simulations, which is the focus of this paper, explores the effect of code-coupling frequency. These simulations include initial SOLPS solutions converged to the inter-ELM state, ion impact energy ( E in ) and angles ( A in ) calculated by hPIC2, and an improved heat transfer description in Xolotl. The model predicts increases in particle fluxes and decreases in heat fluxes by 10%–20% with the coupling time-step. Compared with the first set of simulations, the less shallow impact angle leads to smaller reflection rates and significant D implantation. The higher fraction of implanted flux (and deeper), in particular during ELMs, increases the accumulated D content in the W near-surface region. Future expansion of the workflow includes coupling to hPIC2 and GITR to ensure accurate descriptions of E in and A in , and W impurity transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Sensitivities of time-dependent temperature profile predictions for NSTX with the multi-mode model

The Multi-Mode Model (MMM) for turbulent transport was applied to a large set of well-analyzed discharges from the National Spherical Torus Experiment (NSTX) in order to evaluate its sensitivities to a wide range of plasma conditions. MMM calculations were performed for hundreds of milliseconds in each discharge by performing time-dependent predictive simulations with the 1.5D tokamak integrated modeling code TRANSP. A closely related study (Lestz et al 2025 Plasma Phys. Control. Fusion 67 105029) concluded that MMM predicted electron and ion temperature profiles that were in reasonable agreement with NSTX observations, generally outperforming a different reduced transport model, TGLF. This finding motivates the more thorough investigation of the characteristics of the MMM predictions conducted in this work. The simulations with MMM have electron energy transport dominated by electron temperature gradient modes in the examined discharges with relatively low plasma β (ratio of kinetic plasma pressure to magnetic field pressure) and high collisionality, transitioning to a mixture of different modes for higher β and lower collisionality. The thermal ion diffusivity predicted by MMM is much smaller than the neoclassical contribution, in line with previous experimental analysis of NSTX. Nonetheless, the electron and ion temperature profiles are coupled via collisional energy exchange and thus sensitive to which transport channels are predicted. The time-dependent simulations with MMM are robust to the simulation start time, converging to remarkably similar temperature profiles later during the discharge. MMM typically overpredicts confinement relative to NSTX observations, leading to the prediction of overly steep temperature profiles. Plasmas with spatially broader temperature profiles, higher plasma β, and longer energy confinement times tend to be predicted by MMM with better agreement with the experiment. As a result, these findings provide useful context for understanding the regime-dependent tendencies of MMM in anticipation of self-consistent, time-dependent predictive simulations of NSTX-U discharges with these same modeling tools.

MMM↗

Importance of Electron Correlation on the Geometry and Electronic Structure of [2Fe–2S] Systems: A Benchmark Study of the [Fe 2 S 2 (SCH 3 ) 4 ] 2–,3–,4– , [Fe 2 S 2 (SCys) 4 ] 2– , [Fe 2 S 2 (S- p -tol) 4 ] 2– , and [Fe 2 S 2 (S- o -xyl) 4 ] 2– Complexes

Iron–sulfur clusters are crucial for biological electron transport and catalysis. Obtaining accurate geometries, energetics, manifolds of their excited electronic states, and reduction energies is important to understand their role in these processes. Here, using a [2Fe–2S] model complex with Fe II and Fe III oxidation states, which leads to different charges, i.e., [Fe 2 S 2 (SMe) 4 ] 2–,3–,4– , we benchmarked a variety of computational methodologies ranging from density functional theory (DFT) to post-Hartree–Fock methods, including complete active space self-consistent field (CASSCF), multireference configuration interaction, the second-order N-electron valence state perturbation theory (NEVPT2), and the linearized integrand approximation of adiabatic connection (AC0) approaches. Additionally, we studied three experimentally well-characterized complexes, [Fe 2 S 2 (SCys) 4 ] 2– , [Fe 2 S 2 (S-o-tol) 4 ] 2– , and [Fe 2 S 2 (S-o-xyl) 4 ] 2– , via DFT methods. We conclude that the dynamic electron correlation is important for accurately predicting the geometry of these complexes. Broken symmetry (BS) DFT correctly predicts experimental geometries of low-spin multiplicity, while CASSCF does not. However, BS-DFT significantly overestimates the difference between the low- and high-spin electronic states for a given oxidation state. At the same time, CASSCF underestimates it but provides relative energies closer to the reference NEVPT2 results. Finally, AC0 provides energetics of NEVPT2 quality with the additional advantage of being able to use large CASSCF sizes. NEVPT2 gives the best estimates of the Fe III /Fe III → Fe II /Fe III (4.27 eV) and Fe II /F III → Fe II /F II (7.72 eV) reduction energies. The results provide insight into the electronic structure of these complexes and assist in the understanding of their physical properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strategies to Obtain Reliable Energy Landscapes from Embedded Multireference Correlated Wavefunction Methods for Surface Reactions

Embedded correlated wavefunction (ECW) theory is a powerful tool for studying ground- and excited-state reaction mechanisms and associated energetics in heterogeneous catalysis. Several factors are important to obtaining reliable ECW energies, critically the construction of consistent active spaces (ASs) along reaction pathways when using a multireference correlated wavefunction (CW) method that relies on a subset of orbital spaces in the configuration interaction expansion to account for static electron correlation, e.g., complete AS self-consistent field theory, in addition to the adequate partitioning of the system into a cluster and environment, as well as the choice of a suitable basis set and number of states included in excited-state simulations. Here, in this work, we conducted a series of systematic studies to develop best-practice guidelines for ground- and excited-state ECW theory simulations, utilizing the decomposition of NH 3 on Pd(111) as an example. We determine that ECW theory results are relatively insensitive to cluster size, the aug-cc-pVDZ basis set provides an adequate compromise between computational complexity and accuracy, and that a fixed-clean-surface approximation holds well for the derivation of the embedding potential. Additionally, we demonstrate that a merging approach, which involves generating ASs from the molecular fragments at each configuration, is preferable to a creeping approach, which utilizes ASs from adjacent structures as an initial guess, for the generation of consistent potential energy curves involving open-d-shell metal surfaces, and, finally, we show that it is essential to include bands of excited states in their entirety when simulating excited-state reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phonon dynamics in the chiral Kitaev spin liquid

Here, we investigate the effect of a magnetic field on the extended Kitaev spin-liquid state through phonon dynamics. Using a constrained fermionic self-consistent mean field method, we analyze the quantum spin liquid (QSL) ground state for the extended Kitaev model with both the Zeeman term and the perturbative three-spin interaction term 𝜅. Our results demonstrate the dependence of the stability of the Kitaev QSL state on the field direction, consistent with findings in the literature. Additionally, we calculate the phonon dynamics for acoustic phonons coupled to the Majorana fermion excitations of the Kitaev spin-liquid state, discussing the temperature and field evolution of these quantities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗