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At least 127 records · Page 7

Magic-angle twisted symmetric trilayer graphene as a topological heavy-fermion problem

Recently, Song and Bernevig [Phys. Rev. Lett. 129, 047601 (2022)] reformulated magic-angle twisted bilayer graphene as a topological heavy fermion problem, and used this reformulation to provide a deeper understanding for the correlated phases at integer fillings. Here, in this work, we generalize this heavy-fermion paradigm to magic-angle twisted symmetric trilayer graphene, and propose a low-energy f–c–d model that reformulates magic-angle twisted symmetric trilayer graphene as heavy localized f modes coupled to itinerant topological semimetalic c modes and itinerant Dirac d modes. Our f–c–d model well reproduces the single-particle band structure of magic-angle twisted symmetric trilayer graphene at low energies for displacement field $\mathcal{E}$ ϵ [0,300]⁢ meV. By performing Hartree-Fock calculations with the f–c–d model for v = 0,–1,–2 electrons per Moiré unit cell, we reproduce all the correlated ground states obtained from the previous numerical Hartree-Fock calculations with the Bistritzer-MacDonald-type model, and we find additional new correlated ground states at high displacement field. Based on the numerical results, we propose a simple rule for the ground states at high displacement fields by using the f–c–d model, and provide analytical derivation for the rule at charge neutrality. We also provide analytical symmetry arguments for the (nearly) degenerate energies of the high-$\mathcal{E}$ ground states at all the integer fillings of interest, and make experimental predictions of which charge-neutral states are stabilized in magnetic fields. Our f–c–d model provides a new perspective for understanding the correlated phenomena in magic-angle twisted symmetric trilayer graphene, suggesting that the heavy fermion paradigm of Song and Bernevig [Phys. Rev. Lett. 129, 047601 (2022)] should be the generic underpinning of correlated physics in multilayer moire graphene structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Approximate spin projection of three-component UHF wavefunctions - The states of the pentachlorocyclopentadienyl cation and the croconate dianion, C5O5/2-/

The approximate spin projection method of Amos et al. is extended to handle UHF wave functions having three significant components of differing multiplicity. An expression is given for the energy after single annihilation which differs from that of Amos and Hall. The new expression reproduces the results obtained from a previous exact calculation for which the weights and energies of the components are known. The extended approximate projection method is applied to the pi-electron UHF wave functions for the ground states of the pentachlorocyclopentadienyl cation and the croconate dianion, C5O5(2-). The results indicate a triplet ground state for the former and a singlet ground state for the latter, in agreement with experimental ESR susceptibility measurements for these molecular ions. C5C15(-) cannont be treated by restricted Hartree-Fock theory, due to its open-shell ground state. Incorrect results are obtained for the croconate dianion, if restricted Hartree-Fock theory and singly excited configuration interactions are utilized.

Phillips, D. H.↗

I ntera C hem : Exploring Excited States in Virtual Reality with Ab Initio Interactive Molecular Dynamics

InteraChem is an ab initio interactive molecular dynamics (AI-IMD) visualizer that leverages recent advances in virtual reality hardware and software, as well as the graphical processing unit (GPU)-accelerated TeraChem electronic structure package, in order to render quantum chemistry in real time. We introduce the exploration of electronically excited states via AI-IMD using the floating occupation molecular orbital-complete active space configuration interaction method. The optimization tools in InteraChem enable identification of excited state minima as well as minimum energy conical intersections for further characterization of excited state chemistry in small- to medium-sized systems. We demonstrate that finite-temperature Hartree–Fock theory is an efficient method to perform ground state AI-IMD. InteraChem allows users to track electronic properties such as molecular orbitals and bond order in real time, resulting in an interactive visualization tool that aids in the interpretation of excited state chemistry data and makes quantum chemistry more accessible for both research and educational purposes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shake loss intensities in x-ray photoelectron spectroscopy: Theory, experiment, and atomic composition accuracy for MgO and related compounds

The relative intensities of XPS core levels, scaled by their photoionization cross sections, are regularly used to determine sample atomic composition. Cross sections, however, give the intensity to all possible final states for the core ionizations, not just to the main peak. This includes all intrinsic satellite structure (shake states and, for open shell systems, the different ionic multiplets). In practice, for solids, this is usually experimentally impossible to determine accurately because such a satellite structure sits on the inelastically scattered electron background and cannot be easily separated. Therefore, usually, only the intensity of the main peak is used. This limits the ultimate possible accuracy of XPS composition determination. The purpose of the present paper is to examine the contributions that a theoretical analysis of losses of intensity can make to improve quantitation. For an MgO single crystal, we show that the correct stoichiometry of 1:1 can be recovered using the theoretical analysis of the experimental MgO peak ratio intensities. For materials with a sufficient bandgap for the XPS main peaks to be separated from the scattered background, the intensity of main peaks can often be accurately determined. Thus, if one uses theory to calculate that fraction of the total intensity lost from a main peak into all its satellite structure, the intensity of just main peaks could then be used to more accurately determine relative atom % composition. This work tests this approach using a single crystal MgO (50% Mg, 50% O) standard. Ab initio electronic structure theory of representative MgO clusters is used to determine Hartree–Fock wave functions for the ground state and final ionized states corresponding to the main Mg 2p and O1s XPS peaks of the oxide. The sudden approximation, SA, is used to determine the fractional losses from these main peaks to shake satellites, which is found to be greater for O1s than Mg2p. This results in predicted “apparent composition” for stoichiometric MgO of 55.2% Mg, 44.8% O instead of the true 50% Mg, 50% O. Equivalent theory for CaO results in a predicted apparent Ca value of 53.4%. Experimentally, using Mg2s or 2p intensity ratio to O1s, we find values between 52.2% and 56.0% Mg using two crystals and four different instrument electron pass energies. The average value of the measurements is 54.5% Mg when corrected for the presence of an adventitious carbon overlayer and slight surface hydroxide. Though this agreement with theory may be somewhat fortuitous, given the potential experimental errors, which are fully discussed, it is similar to that in our earlier study on LiF. We also present preliminary experimental data on Mg(OH) 2 and MgSO 4 , which show a similar trend of apparently higher than 50% Mg, but we have no theory values. We are not yet able to experimentally test for validation of the difference between apparent composition for MgO (55.2% Mg) and CaO (53.4% Ca), owing to significant carbonate formation at the surface of the single crystal CaO. Here, an important conclusion is that the theoretical determination of shake losses, obtained with ab initio wavefunctions and the SA, is likely to be a useful way to calibrate the accuracy and reliability of compositions obtained from XPS intensities and merits further study.

47 OTHER INSTRUMENTATION↗

Photoabsorption in formaldehyde

Theoretical studies of the vertical electronic dipole excitation and ionization spectra in molecular formaldehyde are reported. The investigations relied on configuration-interaction calculations and moment-theory techniques. A double-zeta basis of contracted Gaussian-lobe functions supplemented with appropriate polarization and bond functions was used to construct Fock spectra in C(2 nu) symmetry for certain states near the ground state equilibrium geometry. The ionization energies, discrete vertical transition frequencies, and oscillator strengths for occupied and vertical Fock orbitals are in general accord with experimental determinations and other theoretical calculations. Stieltjes and Chebyshev vertical electronic photoionization profiles were calculated and found to be in good agreement with appropriately averaged photoionization-mass spectrometric measurements of the cross section for parent H2CO(+) ion production.

Langhoff, P. W.↗

Nature of the Correlated Insulator States in Twisted Bilayer Graphene

We use self-consistent Hartree-Fock calculations performed in the full $\pi$-band Hilbert space to assess the nature of the recently discovered correlated insulator states in magic-angle twisted bilayer graphene (TBG). In this work, we find that gaps between the flat conduction and valence bands open at neutrality over a wide range of twist angles, sometimes without breaking the system’s valley projected $\mathcal{C}_2\mathcal{T}$ symmetry. Broken spin-valley flavor symmetries then enable gapped states to form not only at neutrality, but also at total moiré band filling $\textit{n}$ = ± $\textit{p}/4$ with integer $\textit{p}$ = 1, 2, 3, when the twist angle is close to the magic value at which the flat bands are most narrow. Because the magic-angle flat band quasiparticles are isolated from remote band quasiparticles only for effective dielectric constants larger than ~20, the gapped states do not necessarily break $\mathcal{C}_2\mathcal{T}$ symmetry and as a consequence the insulating states at $\textit{n}$ = ± 1/ 4 and $\textit{n}$ = ± 3/4 need not exhibit a quantized anomalous Hall effect.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Comparing correlation components and approximations in Hartree–Fock and Kohn–Sham theories via an analytical test case study

The asymmetric Hubbard dimer is a model that allows for explicit expressions of the Hartree–Fock (HF) and Kohn–Sham (KS) states as analytical functions of the external potential, Δv, and of the interaction strength, U. We use this unique circumstance to establish a rigorous comparison between the individual contributions to the correlation energies stemming from the two theories in the {U, Δv} parameter space. Within this analysis of the Hubbard dimer, we observe a change in the sign of the HF kinetic correlation energy, compare the indirect repulsion energies, and derive an expression for the “traditional” correlation energy, i.e., the one that corrects the HF estimate, in a pure site-occupation function theory spirit [Eq. (45)]. Next, we test the performances of the Liu–Burke and the Seidl–Perdew–Levy functionals, which model the correlation energy based on its weak- and strong-interaction limit expansions and can be used for both the traditional and the KS correlation energies. Further, our results show that, in the Hubbard dimer setting, they typically work better for the HF reference, despite having been originally devised for KS. These conclusions are somewhat in line with prior assessments of these functionals on various chemical datasets. However, the Hubbard dimer model allows us to show the extent of the error that may occur in using the strong-interaction ingredient for the KS reference in place of the one for the HF reference, as has been carried out in most of the prior assessments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Weak-coupling theory of neutron scattering as a probe of altermagnetism

Inelastic neutron scattering provides a powerful probe of the magnetic excitations of quantum magnets. Altermagnets have recently emerged as a new class of magnets with vanishing net magnetization characteristic of antiferromagnets and with a spin-split electronic structure typical of ferromagnets. Here we introduce a minimal Hubbard model with two-sublattice orthorhombic anisotropy as a framework to study altermagnetism. Using unrestricted Hartree-Fock calculations, we find an altermagnetic state for this model that evolves from a metallic state to an insulating state with increasing Hubbard-U Coulomb repulsion. We then examine the inelastic neutron scattering response in these states using random-phase approximation calculations of the dynamic spin susceptibility χ"(q,ω). We find that the magnetic excitation spectrum depends on its chirality for q along certain directions in reciprocal space, an observation that may be used in inelastic neutron scattering experiments as a probe of altermagnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Energy density functional and sensitivity of energies of giant resonances to bulk nuclear matter properties

The development of a modern and more realistic nuclear energy density functional (EDF) for accurate predictions of properties of nuclei is the subject of enhanced activity, since it is very important for the study of properties of nuclear matter (NM), giant resonances and, in particular, of properties of rare nuclei with unusual neutron-to-proton ratios. Here, we provide a short review of the current status of the nuclear EDF and the theoretical results obtained for properties of nuclei and nuclear matter. We will first describe a method for determining the parameters of the EDF, associated with the Skyrme type effective interaction, by carrying out a Hartree-Fock based fit to extensive set of data of ground state properties and constraints. Next we will describe the fully self-consistent Hartree-Fock (HF) based random-phase-approximation (RPA) theory for calculating the strength functions S(E) and centroid energies E CEN of giant resonances and the folding model (FM) distorted wave Вorn approximation (DWBA) to calculate the excitation cross section of giant resonances by α scattering. Then we will provide results for: (i) the Skyrme parameters of the KDE0v1 EDF; (ii) consequences of violation of self-consistently in HF-based RPA; (iii) FM-DWBA calculation of excitation cross section; (iv) values of the E CEN of isoscalar and isovector giant resonances of multipolarities L=0–3 for a wide range of spherical nuclei, using 33 EDFs associated with standard form of the Skyrme type interactions, commonly employed in the literature; and (v) the sensitivities E CEN of the giant resonances to bulk properties of NM. We also determine constraints on NM properties, such as the incompressibility coefficient and effective mass, by comparing with experimental data on E CEN of giant resonances.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Quantum-classical electron distributions in atoms and atomic ions

A quantum-classical approach is used to obtain the velocity distributions in atoms and positive and negative ions in both ground and excited states. In the analysis, Hartree-Fock electronic wavefunctions are used to determine the radial electron distributions, and the central-field approximation is used to study the the dynamic properties of the localized electrons. The distributions for the outer and inner shells are found to agree well with exact results obtained by numerical calculations.

Kunc, Joseph A.↗

Origin of the magnetic and orbital ordering in α-Sr 2 CrO 4

Motivated by recent experimental progress in transition metal oxides with the K 2 NiF 4 structure, in this study we investigate the magnetic and orbital ordering in α-Sr 2 CrO 4 . Using first principles calculations, first we derive a three-orbital Hubbard model, which reproduces the ab initio band structure near the Fermi level. The unique reverse splitting of t 2g orbitals in α-Sr 2 CrO 4 , with the 3d 2 electronic configuration for the Cr 4+ oxidation state, opens up the possibility of orbital ordering in this material. Using real-space Hartree-Fock for multi-orbital systems, we constructed the ground state phase diagram for the two dimensional compound α-Sr 2 CrO 4 . We found stable ferromagnetic, antiferromagnetic, antiferro-orbital, and staggered orbital stripe ordering in robust regions of the phase diagram. Furthermore, using the density matrix renormalization group method for two-leg ladders with the realistic hopping parameters of α-Sr 2 CrO 4 , we explore magnetic and orbital ordering for experimentally relevant interaction parameters. Again, we find a clear signature of antiferromagnetic spin ordering along with antiferro-orbital ordering at moderate to large Hubbard interaction strength. We also explore the orbital-resolved density of states with Lanczos, predicting insulating behavior for the compound α-Sr 2 CrO 4 , in agreement with experiments. Finally, an intuitive understanding of the results is provided based on a hierarchy between orbitals, with d xy driving the spin order, while electronic repulsion and the effective one dimensionality of the movement within the d xz and d yz orbitals driving the orbital order.

36 MATERIALS SCIENCE↗

Average Rényi entanglement entropy in Gaussian boson sampling

Recently, many experiments have been conducted with the goal of demonstrating a quantum advantage over classical computation. One popular framework for these experiments is Gaussian boson sampling, where quadratic photonic input states are interfered via a linear optical unitary and subsequently measured in the Fock basis. In this paper, we study the modal entanglement of the output states in this framework just before the measurement stage. Specifically, we compute Page curves as measured by various Rényi- α entropies, where the Page curve describes the entanglement between two partitioned groups of output modes averaged over all linear optical unitaries. We derive these formulas for α = 1 (i.e., the von Neumann entropy) and, more generally, for all positive integer α , in the asymptotic limit of infinite number of modes and for input states that are composed of single-mode-squeezed-vacuum state with equal squeezing strength. We then analyze the limiting behaviors when the squeezing is small and large. Having determined the averages, we then explicitly calculate the Rényi- α variance for integers α > 1 and are able to show that these entropies are weakly typical. Published by the American Physical Society 2025

Youm, Jason (ORCID:0009000057597782)↗

Excited States of Crystalline Point Defects with Multireference Density Matrix Embedding Theory

Accurate and affordable methods to characterize the electronic structure of solids are important for targeted materials design. Embedding-based methods provide an appealing balance in the trade-off between cost and accuracy-particularly when studying localized phenomena. Here, we use the density matrix embedding theory (DMET) algorithm to study the electronic excitations in solid-state defects with a restricted open-shell Hartree-Fock (ROHF) bath and multireference impurity solvers, specifically, complete active space self-consistent field (CASSCF) and n-electron valence state second-order perturbation theory (NEVPT2). In this work, we apply the method to investigate the electronic excitations in an oxygen vacancy (OV) on a MgO(100) surface and find absolute deviations within 0.05 eV between DMET using the CASSCF/NEVPT2 solver, denoted as CAS-DMET/NEVPT2-DMET, and the nonembedded CASSCF/NEVPT2 approach. Next, we establish the practicality of DMET by extending it to larger supercells for the OV defect and a neutral silicon vacancy in diamond where the use of nonembedded CASSCF/NEVPT2 is extremely expensive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Detecting Symmetry Breaking in Magic Angle Graphene Using Scanning Tunneling Microscopy

A growing body of experimental work suggests that magic angle twisted bilayer graphene exhibits a "cascade" of spontaneous symmetry-breaking transitions, sparking interest in the potential relationship between symmetry breaking and superconductivity. However, it has proven difficult to find experimental probes which can unambiguously identify the nature of the symmetry breaking. Here, we show how atomically resolved scanning tunneling microscopy can be used as a fingerprint of symmetry-breaking order. Further, by analyzing the pattern of sublattice polarization and "Kekulé" distortions in small magnetic fields, order parameters for each of the most competitive symmetry-breaking states can be identified. In particular, we show that the "Kramers intervalley coherent state," which theoretical work predicts to be the ground state at even integer fillings, shows a Kekulé distortion which emerges only in a magnetic field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Theoretical study of the X1Sigma(+) states of the alkali hydrides NaH-CsH

By means of near Hartree-Fock quality Slater basis sets, and the incorporation of electron correlation through the coupled-pair formalism, theoretical potentials are obtained for the X1Sigma(+) states of NaH, KH, and RbH. Electric dipole moment functions are given for NaH-RbH, as well as vibrationally averaged dipole moments, Einstein coefficients, and radiative lifetimes for the first 10 vibrational levels; an extensive study is made of the computational requirements for an accurate permanent dipole moment of KH.

Langhoff, Stephen R.↗

Probing neutron-skin thickness with free spectator neutrons in ultracentral high-energy isobaric collisions

We show that the yield ratio of free spectator neutrons produced in high-energy 96 Zr+ 96 Zr to 96 Ru+ 96 Ru collisions is a clean probe of the neutron-skin thickness of colliding nuclei and the slope parameter L of the symmetry energy. The idea is demonstrated based on the proton and neutron density distributions via a state-of-the-art Skyrme-Hartree-Fock-Bogolyubov calculation. Among spectator nucleons given by the Glauber model, free spectator neutrons include those from direct production that survive from clusterization as well as those from deexcitation of heavy clusters described by the popular GEMINI model. More free neutrons are produced in collisions of 96 Zr nucleus due to its larger neutron skin, compared to those produced in collisions of 96 Ru nucleus with a smaller neutron skin. The difference of the free spectator neutron yield is further increased with the increasing difference of the neutron-skin thickness between 96 Zr and 96 Ru with a larger L value, and the increase in ultracentral collisions is particularly insensitive to model details and experimental uncertainties. Since the production of free spectator neutrons is not affected by the complicated dynamics in the mid-rapidity region, the ratio of their multiplicities in ultracentral isobaric collisions is a robust observable for constraining the neutron skin and L value.

79 ASTRONOMY AND ASTROPHYSICS↗