Relativistic Intermolecular Forces
Generalized Breit-Pauli Hamiltonian used to give systematic treatment of magnetic and other relativistic intermolecular energies
ENERGY↗
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Optimizing the Solvent Reorganization Free Energy by Metal Substitution for Nanocage Catalysis
The supramolecular capsule Ga 4 L 6 12– has been found to catalyze a number of important chemical reactions, but the close proximity of a poorly organized external solvent environment can serve as an impediment to the reaction chemistry. Here, using ab initio molecular dynamic calculations and electric field analyses, we find that metal substitution of indium for gallium lowers the total and electrostatic activation barriers by ~3–4 kcal/mol in water solvent. Using an energy decomposition analysis of the interaction of water solvent with the metal vertices, we find that Pauli repulsion between the metal and water decreases, allowing the water coordination with the metal to increase, upon substitution of In for Ga. We therefore determine that the stabilization of the transition state is due to a better arrangement of water molecules around the metal vertices of In 4 L 6 12– and provides a proof of concept of how to redesign the nanocage scaffold in order to reduce the solvent reorganization energy.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
American WAKE experimeNt (AWAKEN)
The American WAKE experimeNt (AWAKEN) is an international multi-institutional wind energy field campaign to better understand wake losses within operational wind farms. Wake interactions are among the least understood physical interactions in wind plants today, leading to unexpected power and profit losses. For example, Ørsted, the world’s largest offshore wind farm developer, recently announced a downward revision in energy estimates across their energy generation portfolio, primarily caused by underprediction of energy losses from wind farm blockage and wakes. In their announcement, they noted that the standard industry models used for their original energy estimates were inaccurate, and this was likely an industry-wide issue. To help further improve and validate wind plant models across scales from individual turbines as well as interfarm interactions between plants, new observations, such as those planned for AWAKEN, are critical. These model improvements will enable both improved layout and more optimal operation of wind farms with greater power production and improved reliability, ultimately leading to lower wind energy costs.
17 WIND ENERGY↗
Effects of Landau quantization on neutrino emission and absorption
Some neutron stars known as magnetars possess very strong magnetic fields, with surface fields as large as 10 15 G and internal fields that are possibly stronger. Recent observations of the radio pulsar GLEAM-X J1627 suggest it may have a surface field as strong as 10 16 G. In the presence of a strong magnetic field, Leinson and Perez showed and Baiko and Yakovlev confirmed that the energy levels of electrons and protons are quantized and the direct Urca process allows neutron stars to cool rapidly, even at low density. For the case of magnetic fields 𝐵 ≳ 10 16 G, we find features in the emissivity due to energy quantization that are not captured by the frequently employed quasiclassical approximation where energy levels are treated as nearly continuous. Resonances can result in amplification of the neutrino emissivity at specific densities compared to a calculation that neglects quantization, particularly at low temperature. These effects are not important for the thermal evolution of an entire neutron star, but may be relevant for phenomena that depend on behavior at specific densities. Here, we present a fully relativistic calculation of the direct Urca rate in a strong magnetic field using the standard V-A weak Lagrangian incorporating mean field nuclear effects and discuss approaches to the numerical challenge the modified wave functions present and a new semianalytic approximation. These tools are also applicable to calculating neutrino opacities in strong magnetic fields in the ejecta of binary neutron star mergers. We calculate the opacities for neutrinos capturing on free nucleons at subsaturation densities and temperatures exceeding an MeV. We find an enhancement to capture processes of the lowest energy neutrinos by an order of magnitude or more due to suppression of electron Pauli blocking in the case of capture on neutrons, and from the effect of the nucleon magnetic moments in the case of capture on protons.
astrophysical electromagnetic fields↗
Tuning the flat bands of the kagome metal CoSn with Fe, In, or Ni doping
We report CoSn is a Pauli paramagnet with relatively flat d bands centered about 100 meV below the Fermi energy, E F . Single crystals of CoSn lightly doped with Fe, In, or Ni are investigated using x-ray and neutron scattering, magnetic susceptibility and magnetization, AC susceptibility, specific heat, and resistivity measurements. Within the rigid-band approximation, hole doping with a few percent of Fe or In should move the flat bands closer to E F , whereas electron doping with Ni should move the flat bands further away from E F . We provide evidence that this indeed occurs. Fe and In doping drive CoSn toward magnetism, while Ni doping suppresses CoSn's already weak magnetic response. The resulting ground state is different for Fe versus In doping. For Fe-doped crystals, Co 1-x Fe x Sn, with 0.02< x <0.27, the magnetic and specific-heat data are consistent with the formation of a spin glass, with a glass temperature, T g , ranging from 1 K for x = 0.02 to 10 K for x = 0.27. Powder and single-crystal neutron diffraction found no evidence of long-range magnetic order below T g for samples with x ≈ 0.17. For In-doped crystals, CoSn 1-y In y , both the magnetic susceptibility and the Sommerfeld coefficient, γ, increase substantially relative to pure CoSn, but with no clear indication of a magnetic transition for 0.05< y <0.2. CoSn crystals doped with Ni (Co 0.93 Ni 0.07 Sn) have a significantly smaller magnetic susceptibility and γ than pure CoSn, consistent with flat bands further from E F .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)–Cyclobutadiene Complex
Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)-cyclobutadiene complex, accompanied with bonding analysis by state-of-the-art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)-bonding by comparison of the gold(I)-cyclobutadiene to congeners stabilized by p-, d-, and f-block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Finally, Pauli repulsion is similarly determined as a significant interaction in Au I -alkyne species, corroborating this revised understanding of Au I bonding.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Real-Time Operator Evolution in Two and Three Dimensions via Sparse Pauli Dynamics
We study real-time operator evolution using sparse Pauli dynamics, a recently developed method for simulating expectation values of quantum circuits. On the examples of energy and charge diffusion in one-dimensional (1D) spin chains and sudden quench dynamics in the 2D transverse-field Ising model, it is shown that this approach can compete with state-of-the-art tensor network methods. We further demonstrate the flexibility of the approach by studying quench dynamics in the 3D transverse-field Ising model that is highly challenging for tensor network methods. For the simulation of expectation value dynamics starting in a computational basis state, we introduce an extension of sparse Pauli dynamics that truncates the growing sum of Pauli operators by discarding terms with a large number of X and Y matrices. This is validated by our 2D and 3D simulations. Finally, we argue that sparse Pauli dynamics is not only capable of converging challenging observables to high accuracy, but can also serve as a reliable approximate approach even when given only limited computational resources. Published by the American Physical Society 2025
Begušić, Tomislav (ORCID:0000000279424134)↗
The nature of the chemical bond and the role of non-dynamical and dynamical correlation in Be2
In the spin-coupled generalized valence bond (SCGVB) description of Be2, there is a pair of electrons in highly overlapping “inner” orbitals corresponding to a traditional σ bond, but this bond is compromised by Pauli repulsion arising from its overlap with a second “outer” pair. The presence of this outer pair of electrons leads to a repulsive potential energy curve at long range and a bound, but metastable molecule at short range. To obtain further insights into the nature of the bond in Be2, we determined the non-dynamical and dynamical correlation contributions to the potential energy curve of Be2 using four different choices for the zero-order wave function: Restricted Hartree–Fock (RHF), SCGVB, valence-CASSCF(4,4), and valence-CASSCF(4,8). The SCGVB and valence-CASSCF(4,4) wave functions yield similar breakdowns of the total correlation energy, with non-dynamical correlation being the more important contribution. For the RHF and valence-CASSCF(4,8) wave functions, dynamical correlation is critical, without which the potential energy curve is purely repulsive. High accuracy calculations on the HBen−1Be–BeBen−1H molecule as a function of n (n = 1–6) suggest that the intrinsic strength of a Be–Be σ bond uncompromised by Pauli repulsion is on the order of 62–63 kcal/mol, and its length is 2.13–2.14 Å, ∼60 kcal/mol stronger and ∼0.35 Å shorter than in Be2.
Xu, Lu. T. (ORCID:0000000182064902)↗
Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)‐Cyclobutadiene Complex
Abstract Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)‐cyclobutadiene complex, accompanied with bonding analysis by state‐of‐the‐art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)‐bonding by comparison of the gold(I)‐cyclobutadiene to congeners stabilized by p‐, d‐, and f‐block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Pauli repulsion is similarly determined as a significant interaction in Au I ‐alkyne species, corroborating this revised understanding of Au I bonding.
Wong, Zeng Rong↗
Gate-tunable modulation of the optical properties of multilayer graphene by the reversible intercalation of ionic liquid anions
We demonstrate a substantial modulation of the optical properties of multilayer graphene (~100 layers) using a simple device consisting of a multilayer graphene/polymer electrolyte membrane/gold film stack. Applying a voltage of 3–4 V drives the intercalation of anion [TFSI] - [ion liquid diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide [DEME][TFSI]] resulting in the reversible modulation of the properties of this optically dense material. Upon intercalation, we observe an abrupt shift of 35 cm -1 in the G band Raman mode, an abrupt increase in FTIR reflectance over the wavelength range from 1.67 to 5 $μ$m (2000–6000 cm -1 ), and an abrupt increase in luminescent background observed in the Raman spectra of graphene. Furthermore, all of these abrupt changes in the optical properties of this material arise from the intercalation of the TFSI - ion and the associated change in the free carrier density (Δ$n$ = 10 20 cm -3 ). Suppression of the 2D band Raman mode observed around 3 V corresponds to Pauli blocking of the double resonance Raman process and indicates a modulation of the Fermi energy of Δ$E$ F = 1.1 eV.
42 ENGINEERING↗
Polarizable Water Potential Derived from a Model Electron Density
A new empirical potential for efficient, large scale molecular dynamics simulation of water is presented. The HIPPO (Hydrogen-like Intermolecular Polarizable POtential) force field is based upon the model electron density of a hydrogen-like atom. This framework is used to derive and parametrize individual terms describing charge penetration damped permanent electrostatics, damped polarization, charge transfer, anisotropic Pauli repulsion, and damped dispersion interactions. Initial parameter values were fit to Symmetry Adapted Perturbation Theory (SAPT) energy components for ten water dimer configurations, as well as the radial and angular dependence of the canonical dimer. The SAPT-based parameters were then systematically refined to extend the treatment to water bulk phases. The final HIPPO water model provides a balanced representation of a wide variety of properties of gas phase clusters, liquid water, and ice polymorphs, across a range of temperatures and pressures. This water potential yields a rationalization of water structure, dynamics, and thermodynamics explicitly correlated with an ab initio energy decomposition, while providing a level of accuracy comparable or superior to previous polarizable atomic multipole force fields. The HIPPO water model serves as a cornerstone around which similarly detailed physics-based models can be developed for additional molecular species.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultrafast photo-induced phonon hardening due to Pauli blocking in MAPbI 3 single-crystal and polycrystalline perovskites
Metal-halide perovskite semiconductors have attracted intense interest over the past decade, particularly for applications in photovoltaics. Low-energy optical phonons combined with significant crystal anharmonicity play an important role in charge-carrier cooling and scattering in these materials, strongly affecting their optoelectronic properties. We have observed optical phonons associated with Pb–I stretching in both MAPbI 3 single crystals and polycrystalline thin films as a function of temperature by measuring their terahertz conductivity spectra with and without photoexcitation. An anomalous bond hardening was observed under above-bandgap illumination for both single-crystal and polycrystalline MAPbI 3 . First-principles calculations reproduced this photo-induced bond hardening and identified a related lattice contraction (photostriction), with the mechanism revealed as Pauli blocking. For single-crystal MAPbI 3 , phonon lifetimes were significantly longer and phonon frequencies shifted less with temperature, compared with polycrystalline MAPbI 3 . We attribute these differences to increased crystalline disorder, associated with grain boundaries and strain in the polycrystalline MAPbI 3 . Thus we provide fundamental insight into the photoexcitation and electron–phonon coupling in MAPbI 3 .
36 MATERIALS SCIENCE↗
Oscillator Strengths for Fine-Structure Transitions in S III
Oscillator strengths and transition probabilities for transitions among the fine-structure levels of the terms belonging to the 3s(sup 2)3p(sup 2), 3s3p(sup 3), 3s(sup 2)3p3d, 3s(sup 2)3p4s, 3s(sup 2)3p4p, and 3s(sup 2)3p4d configurations of S III are calculated using extensive configuration-interaction wave functions. The relativistic effects in intermediate coupling are incorporated by means of the Breit-Pauli Hamiltonian. Small adjustments to the diagonal elements of the Hamiltonian matrices have been made so that the energy splittings are as close as possible to the experimental values. The present results are compared with other available calculations and experiments.
Tayal, S. S.↗
American WAKE experimeNt (AWAKEN)
The national laboratories, directed by the U.S. Department of Energy Wind Energy Technologies Office, will organize, design, and execute a landmark international wake observation and validation campaign known as the American WAKE experimeNt or AWAKEN. This document describes the vision and purpose for AWAKEN and describes some of the organizational activities that have taken place to date. The driving need for this experimental campaign is that wake interactions are among the least understood physical phenomena in wind plants today, leading to unexpected power and financial losses. New observation data gathered will be used to further validate wind plant models and lead to both improved layout and more optimal operation of wind farms with greater power production and improved reliability, ultimately leading to lower wind energy costs. This campaign will occur in the U.S. Midwest, where the largest concentration of wind farms in the U.S. is located and where significant future growth is most likely. The field campaign will provide a data set that is unique among wake studies, based on location, scope, and observational fidelity: most wake studies have largely focused on offshore wind farms, which are not currently critical to the U.S. wind energy supply, and with a limited number of observations. While AWAKEN is focused on land-based wind farms in flat terrain, many of the observations will help researchers understand fundamental wake behavior applicable in both offshore and complex terrain environments.
17 WIND ENERGY↗
Computational modeling of charge hopping dynamics along a disordered one-dimensional wire with energy gradients in quantum environments
This computational study investigates the effects of energy gradients on charge hopping dynamics along a one-dimensional chain of discrete sites coupled to quantum bath, which is modeled at the level of Pauli master equation (PME). This study also assesses the performance of different approximations for the hopping rates. Three different methods for solving the PME, a fourth order Runge–Kutta method, numerical diagonalization of the rate matrix followed by analytic propagation, and kinetic Monte Carlo simulation method, are tested and confirmed to produce virtually identical values of time dependent mean square displacement, diffusion constant, and mobility. Five different rate expressions, exact numerical evaluation of Fermi’s Golden Rule (FGR) rate, stationary phase interpolation (SPI) approximation, semiclassical approximation, classical Marcus rate, and Miller–Abrahams rate, are tested to help understand the effects of approximations in representing quantum environments in the presence of energy gradients. The results based on direct numerical evaluation of FGR rate exhibit transition from diffusive to non-diffusive behavior with the increase in the gradient and show that the charge transport in the quantum bath is more sensitive to the magnitude of the gradient and the disorder than in the classical bath. Among all the four approximations for the hopping rates, the SPI approximation is confirmed to work best overall. A comparison of two different methods to calculate the mobility identifies drift motion of the population distribution as the major source of non-diffusive behavior and provides more reliable information on the contribution of quantum bath.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Interplay of Pauli Repulsion, Electrostatics, and Field Inhomogeneity for Blueshifting and Redshifting Vibrational Probe Molecules
Many molecules' vibrational frequencies are sensitive to intermolecular electric fields, enabling them to probe the field in complex molecular environments. However, it is often unclear whether the probe is responding to the local electric field or other types of intermolecular interactions, inhibiting interpretation of the frequency and effectiveness as probes. This is especially true for molecules whose vibrational frequencies blueshift instead of the more typical redshift in hydrogen bonding configurations. In this work, we computationally investigate the causes of redshifting versus blueshifting over a range of vibrational reporters. First, we apply adiabatic energy decomposition analysis to a paradigmatic set of probes, finding that redshifting only occurs when electrostatic interactions are strong enough to overcome the dominant and large blueshifting contribution of Pauli repulsion. Furthermore, we demonstrate that field inhomogeneity can further shift the frequency of many probes substantially to either reinforce or counteract the shift expected from a homogeneous field. We find that redshifting is reinforced by electric field inhomogeneity, otherwise field inhomogeneity further weakens the electrostatic contribution relative to Pauli repulsion, leading to blueshifting. Further calculations indicate that the probe's response to field inhomogeneity can be understood by considering the mass of the atoms involved in the stretching mode and sign of the electric field. In explaining the interplay of different intermolecular interactions and field inhomogeneity for many probes, our results should enable the use and interpretation of spectroscopic probes and their connection to electric fields in more complex systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Photoelectrochemical materials for solar energy conversion
Research and development on semiconductors for applications in solar energy conversion has witnessed rapid growth over the past several decades. With the aim of producing chemical fuels from sunlight, intense research efforts have focused on the discovery of semiconductors with crystalline structures and chemical compositions that have the potential to satisfy the complex set of required photoelectrochemical properties. This chapter focuses on the foundational structure-property relationships of selected oxide and nitride semiconductors relevant to their uses as n-/p-type photoelectrodes and as photocatalysts. Their solid-state structures and compositions are described, with a special emphasis on strategies proven effective at targeting suitable band gaps with strong visible-light absorption, efficient charge separation and diffusion of charge carriers, and optimal band edge energies for driving surface redox reactions for water splitting.
O’Donnell, Shaun↗
Many-body expansion for light nuclear systems
Here we extend the many-body expansion (MBE), previously applied to hydrogen bonded and molecular systems, to the light nuclear systems 3 H and 3 He by considering the nucleonic degrees of freedom as fundamental in the expansion. The analysis is based on the Pauli nucleonic dynamics (PND) model, a simple antisymmetrized dynamical code, inspired by the sophisticated constrained molecular dynamics (CoMD) model. The total energy of the 2 H nucleus is calculated with this model at -2.312 MeV, which is within 4% of the experimental value of -2.225 MeV. The application of the MBE yields results for the three-body term in the 3 H nucleus that is comparable with previous estimates, while it is reported for the first time for the nucleus of 3 He . The energies of 3 H and 3 He that include the sum of the one- and two-body terms with the model are - 6.97 ± 0.21 MeV and - 6.19 ± 0.21 MeV and the three-body terms, estimated from the difference of the sum of the one- and two-body terms from the experimentally measured energies, are -1.51 ± 0.21 MeV and -1.53 ± 0.21 MeV, respectively. The MBE for the 3 H and 3 He nuclei is qualitatively similar to the one previously reported for the water trimer: the two- and three-body terms are negative with the latter amounting to ~3% of the former. Additionally, the three-body terms correspond to about 16–23% of the total energy of the bound systems, a percentage that is also comparable to the one in the water trimer (17%). In this manner, the MBE analysis can be applied to light nuclear systems following the same protocol as the one that has been previously extensively used for hydrogen bonded molecular systems.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗