Many-body Calculations Research Articles

Topological properties of single-particle states decaying into a continuum due to interaction

We investigate how topological Chern numbers can be defined when single-particle states hybridize with continua. We do so exemplarily in a bosonic Haldane model at zero temperature with an additional on-site decay of one boson into two and the conjugate fusion of two bosons into one. Restricting the Hilbert space to two bosons at maximum, the exact self-energy is accessible. We use the bilinear Hamiltonian H0 corrected by the self-energy Σ to compute Chern numbers by two different approaches. The results are gauged against a full many-body calculation in the Hilbert space where possible. We establish numerically and analytically that the effective Hamiltonian Heff=H0(k⃗)+Σ(ω,k⃗) reproduces the correct many-body topology if the considered band does not overlap with the continuum. In case of overlaps, one can extend the definition of the Chern number to the non-Hermitian Heff and there is evidence that the Chern number changes at exceptional points. But the bulk-boundary correspondence appears to be no longer valid and edge modes delocalize. Published by the American Physical Society 2024

Renormalized density matrix downfolding: A rigorous framework in learning emergent models from ab initio many-body calculations

Renormalized density matrix downfolding: A rigorous framework in learning emergent models from <i>ab initio</i> many-body calculations

QCManyBody: A flexible implementation of the many-body expansion.

While the many-body expansion (MBE) and counterpoise treatments are commonly used to mitigate the high scaling of accurate abinitio methods, researchers may need to piece together tools and scripts if their primary chosen software does not support targeted features. To further modular software in quantum chemistry, the arbitrary-order, multiple-model-chemistry, counterpoise-enabled MBE implementation from Psi4 has been extracted into an independent, lightweight, and open-source Python module, QCManyBody, with new schema underpinning, application programming interface, and software integrations. The package caters to direct users by facilitating single-point and geometry optimization MBE calculations backed by popular quantum chemistry codes through the QCEngine runner and by defining a schema for requesting and reporting many-body computations. It also serves developers and integrators by providing minimal, composable, and extensible interfaces. The design and flexibility of QCManyBody are demonstrated via integrations with geomeTRIC, OptKing, Psi4, QCEngine, and the QCArchive project.

Symmetry adaptation for self-consistent many-body calculations

The exploitation of space group symmetries in numerical calculations of periodic crystalline solids accelerates calculations and provides physical insight. We present results for a space-group symmetry adaptation of electronic structure calculations within the finite-temperature self-consistent GW method along with an efficient parallelization scheme on accelerators. Our implementation employs the simultaneous diagonalization of the Dirac characters of the orbital representation. Results show that symmetry adaptation in self-consistent many-body codes results in substantial improvements of the runtime, and that block diagonalization on top of a restriction to the irreducible wedge results in additional speedup.

Fermi and Luttinger Arcs: Two Concepts, Realized on One Surface.

We present an analytically solvable model for correlated electrons, which is able to capture the major Fermi surface modifications occurring in both hole- and electron-doped cuprates as a function of doping. The proposed Hamiltonian qualitatively reproduces the results of numerically demanding many-body calculations, here obtained using the dynamical vertex approximation. Our analytical theory provides a transparent description of a precise mechanism, capable of driving the formation of disconnected segments along the Fermi surface (the highly debated "Fermi arcs"), as well as the opening of a pseudogap in hole and electron doping. This occurs through a specific mechanism: The electronic states on the Fermi arcs remain intact, while the Fermi surface part where the gap opens transforms into a Luttinger arc.

Exploring the potential of α-Ge(1 1 1) monolayer in photocatalytic water splitting for hydrogen production

In this study, the structural, electronic, and optical properties of 2D α-Ge(1 1 1) are investigated using Density Functional Theory (DFT) calculations, complemented by many-body perturbation theory calculations based on the GW/BSE approach. The thermodynamic stability of this material is assessed through ab initio molecular dynamics simulations (AIMD), and their dynamic stability is confirmed via phonon dispersion calculations. The analysis of the optical properties reveals significant absorption peaks in both visible and ultraviolet regions, with an absorption edge at 47 eV (1.87 eV without excitonic effects). The band edges are well-aligned with water redox potentials at neutral pH, making them suitable for water-splitting applications. For other pH levels, we find the process may be feasible through the participation of different excited states populated by light absorption. Remarkably, the α-Ge(1 1 1) monolayer demonstrates a predicted solar-to-hydrogen conversion efficiency of 34.80 %, outperforming many other two-dimensional materials. These findings position the α-Ge(1 1 1) monolayer as a promising candidate for developing efficient photocatalytic materials for hydrogen generation via overall water splitting.

Few-femtosecond electron transfer dynamics in photoionized donor-π-acceptor molecules.

The exposure of molecules to attosecond extreme-ultraviolet (XUV) pulses offers a unique opportunity to study the early stages of coupled electron-nuclear dynamics in which the role played by the different degrees of freedom is beyond standard chemical intuition. We investigate, both experimentally and theoretically, the first steps of charge-transfer processes initiated by prompt ionization in prototype donor-π-acceptor molecules, namely nitroanilines. Time-resolved measurement of this process is performed by combining attosecond XUV-pump/few-femtosecond infrared-probe spectroscopy with advanced many-body quantum chemistry calculations. We show that a concerted nuclear and electronic motion drives electron transfer from the donor group on a sub-10-fs timescale. This is followed by a sub-30-fs relaxation process due to the probing of the continuously spreading nuclear wave packet in the excited electronic states of the molecular cation. These findings shed light on the role played by electron-nuclear coupling in donor-π-acceptor systems in response to photoionization.

From Many-Body Ab Initio to Effective Excitonic Models: A Versatile Mapping Approach Including Environmental Embedding Effects.

We present an original multistate projective diabatization scheme based on Green's function formalisms that allows the systematic mapping of many-body ab initio calculations onto effective excitonic models. This method inherits the ability of the Bethe-Salpeter equation to describe Frenkel molecular excitons and intermolecular charge-transfer states equally well, as well as the possibility for an effective description of environmental effects in a QM/MM framework. The latter is found to be a crucial element in order to obtain accurate model parameters for condensed phases and to ensure their transferability to excitonic models for extended systems. The method is presented through a series of examples illustrating its quality, robustness, and internal consistency.

Tensor factorization in ab initio many-body calculations

Tensor factorization in ab initio many-body calculations

Electronic excitations and spin interactions in chromium trihalides from embedded many-body wavefunctions

Although chromium trihalides are widely regarded as a promising class of two-dimensional magnets for next-generation devices, an accurate description of their electronic structure and magnetic interactions has proven challenging to achieve. Here, we quantify electronic excitations and spin interactions in CrX3 (X = Cl, Br, I) using embedded many-body wavefunction calculations and fully generalized spin Hamiltonians. We find that the three trihalides feature comparable d-shell excitations, consisting of a high-spin 4A2(t2g3eg0)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$({t}_{2g}^{3}{e}_{g}^{0})$$\\end{document} ground state lying 1.5–1.7 eV below the first excited state 4T2 (t2g2eg1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${t}_{2g}^{2}{e}_{g}^{1}$$\\end{document}). CrCl3 exhibits a single-ion anisotropy Asia = − 0.02 meV, while the Cr spin-3/2 moments are ferromagnetically coupled through bilinear and biquadratic exchange interactions of J1 = − 0.97 meV and J2 = − 0.05 meV, respectively. The corresponding values for CrBr3 and CrI3 increase to Asia = −0.08 meV and Asia= − 0.12 meV for the single-ion anisotropy, J1 = −1.21 meV, J2 = −0.05 meV and J1 = −1.38 meV, J2 = −0.06 meV for the exchange couplings, respectively. We find that the overall magnetic anisotropy is defined by the interplay between Asia and Adip due to magnetic dipole–dipole interaction that favors in-plane orientation of magnetic moments in ferromagnetic monolayers and bulk layered magnets. The competition between the two contributions sets CrCl3 and CrI3 as the easy-plane (Asia + Adip >0) and easy-axis (Asia + Adip <0) ferromagnets, respectively. The differences between the magnets trace back to the atomic radii of the halogen ligands and the magnitude of spin–orbit coupling. Our findings are in excellent agreement with recent experiments, thus providing reference values for the fundamental interactions in chromium trihalides.

A semiempirical model for low energy electron–atom transport cross sections: The case of noble gases

A semiempirical approach to describe low energy electron–atom transport cross sections of easy implementation and reproduction is presented. The heart of the model is an energy independent two-parameter potential that was adjusted to reproduce the accurate total cross sections for He, Ne, Ar and Kr, measured with a threshold photoelectron source technique from meV up to 20 eV. Once the potential was conceived, the model was validated by comparing the values obtained for the calculated scattering lengths and phase shifts with the respective quantities previously reported in the literature. We close the article by presenting the momentum transfer and viscosity cross sections. Good agreement is found when compared to the similar data obtained from swarm experiments, from phase shifts according to differential cross section measurements and to the cross sections reported by sophisticated ab initio relativistic many-body calculations. Tables for the phase shifts and cross sections are provided for direct use and applications.

Neutrinoless double beta decay in the minimal type-I seesaw model: mass-dependent nuclear matrix element, current limits and future sensitivities

In this work we discuss the neutrino mass dependent nuclear matrix element (NME) of the neutrinoless double beta decay process and derive the limit on the parameter space of the minimal Type-I seesaw model from the current available experimental data as well as the future sensitivities from the next-generation experiments. Both the explicit many-body calculations and naive extrapolations of the mass dependent NME are employed in the current work. The uncertainties of the theoretical nuclear structure models are taken into account. By combining the latest experimental data from 76Ge-based experiments, GERDA and MAJORANA, the 130Te-based experiment, CUORE and the 136Xe-based experiments, KamLAND-Zen and EXO-200, the bounds on the parameter space of the minimal Type-I seesaw model are obtained and compared with the limits from other experimental probes. Sensitivities for future experiments utilizing 76Ge-based (LEGEND-1000), 82Se-based (SuperNEMO), 130Te based (SNO+II) and 136Xe-based (nEXO), with a ten-year exposure, are also derived.

Predicting exciton binding energies from ground-state properties

We systematically investigate the correlations between exciton binding energies and various easily calculated ground-state properties (“predictors”) that have been proposed to correlate with them. We do so for 51 bulk compounds, ranging from simple binary semiconductors to more exotic materials such as noble gas solids, perovskites, and layered systems and show that using only a few easily calculable parameters, a broadly applicable clustering of materials according to their exciton binding energies is possible. While no single one of the proposed parameters satisfactorily predicts the exciton binding energy, a combination of several parameters that enter the Wannier-Mott model or characterize the nature of the valence band and the ionicity of the compound allows a reliable automated clustering of exciton binding energies. The results allow an efficient estimation of the importance of excitonic effects without the need for expensive many-body perturbation theory calculations or other advanced numerically demanding approaches. Published by the American Physical Society 2024

Web-CONEXS: an inroad to theoretical X-ray absorption spectroscopy.

Accurate analysis of the rich information contained within X-ray spectra usually calls for detailed electronic structure theory simulations. However, density functional theory (DFT), time-dependent DFT and many-body perturbation theory calculations increasingly require the use of advanced codes running on high-performance computing (HPC) facilities. Consequently, many researchers who would like to augment their experimental work with such simulations are hampered by the compounding of nontrivial knowledge requirements, specialist training and significant time investment. To this end, we present Web-CONEXS, an intuitive graphical web application for democratizing electronic structure theory simulations. Web-CONEXS generates and submits simulation workflows for theoretical X-ray absorption and X-ray emission spectroscopy to a remote computing cluster. In the present form, Web-CONEXS interfaces with three software packages: ORCA, FDMNES and Quantum ESPRESSO, and an extensive materials database courtesy of the Materials Project API. These software packages have been selected to model diverse materials and properties. Web-CONEXS has been conceived with the novice user in mind; job submission is limited to a subset of simulation parameters. This ensures that much of the simulation complexity is lifted and preliminary theoretical results are generated faster. Web-CONEXS can be leveraged to support beam time proposals and serve as a platform for preliminary analysis of experimental data.

Electronic structure of the strongly correlated electron system plutonium hexaboride: A study from single-particle approximations and many-body calculations.

The electronic structure of the strongly correlated electron system plutonium hexaboride is studied by using single-particle approximations and a many-body approach. Imaginary components of impurity Green's functions show that 5fj=5/2 and 5fj=7/2 manifolds are in conducting and insulating regimes, respectively. Quasi-particle weights and their ratio suggest that the intermediate coupling mechanism is applicable for Pu 5f electrons, and PuB6 might be in the orbital-selective localized state. The weighted summation of occupation probabilities yields the interconfiguration fluctuation and average occupation number of 5f electrons n5f ~ 5.101. The interplay of 5f-5f correlation, spin-orbit coupling, Hund's exchange interaction, many-body transition of 5f configurations, and final state effects might be responsible for the quasiparticle multiplets in electronic spectrum functions. Prominent characters in the density of state, such as the coexistence of atomic multiplet peaks in the vicinity of the Fermi level and broad Hubbard bands in the high-lying regime, suggest that PuB6 could be identified as a Racah material. Finally, the quasiparticle band structure is also presented.

Stability and Redox Mechanisms of Ni-Rich NMC Cathodes: Insights from First-Principles Many-Body Calculations

Stability and Redox Mechanisms of Ni-Rich NMC Cathodes: Insights from First-Principles Many-Body Calculations

Right On Time: Ultrafast Charge Separation Before Hybrid Exciton Formation.

Organic/inorganic hybrid systems offer great potential for novel solar cell design combining the tunability of organic chromophore absorption properties with high charge carrier mobilities of inorganic semiconductors. However, often such material combinations do not show the expected performance: while ZnO, for example, basically exhibits all necessary properties for a successful application in light-harvesting, it wasclearly outpaced by TiO2 in terms of charge separation efficiency. The origin of this deficiency has long been debated. This study employs femtosecond time-resolved photoelectron spectroscopy and many-body ab initio calculations to identify and quantify all elementary steps leading to the suppression of charge separation at an exemplary organic/ZnO interface. It is demonstrated that charge separation indeed occurs efficiently on ultrafast (350fs) timescales, but that electrons are recaptured at the interface on a 100ps timescale and subsequently trapped in a strongly bound (0.7eV) hybrid exciton state with a lifetime exceeding 5µs. Thus, initially successful charge separation is followed by delayed electron capture at the interface, leading to apparently low charge separation efficiencies. This finding provides a sufficiently large time frame for counter-measures in device design to successfully implement specifically ZnO and, moreover, invites material scientists to revisit charge separation in various kinds of previously discarded hybridsystems.

Observation of phonon Stark effect

Stark effect, the electric-field analogue of magnetic Zeeman effect, is one of the celebrated phenomena in modern physics and appealing for emergent applications in electronics, optoelectronics, as well as quantum technologies. While in condensed matter it has prospered only for excitons, whether other collective excitations can display Stark effect remains elusive. Here, we report the observation of phonon Stark effect in a two-dimensional quantum system of bilayer 2H-MoS2. The longitudinal acoustic phonon red-shifts linearly with applied electric fields and can be tuned over ~1 THz, evidencing giant Stark effect of phonons. Together with many-body ab initio calculations, we uncover that the observed phonon Stark effect originates fundamentally from the strong coupling between phonons and interlayer excitons (IXs). In addition, IX-mediated electro-phonon intensity modulation up to ~1200% is discovered for infrared-active phonon A2u. Our results unveil the exotic phonon Stark effect and effective phonon engineering by IX-mediated mechanism, promising for a plethora of exciting many-body physics and potential technological innovations.

Charge density wave ordering in NdNiO2: effects of multiorbital nonlocal correlations

In this work, we investigate collective electronic fluctuations and, in particular, the possibility of the charge density wave ordering in an infinite-layer NdNiO2. We perform advanced many-body calculations for the ab-initio three-orbital model by taking into account local correlation effects, nonlocal charge and magnetic fluctuations, and the electron-phonon coupling. We find that in the considered material, electronic correlations are strongly orbital- and momentum-dependent. Notably, the charge density wave and magnetic instabilities originate from distinct orbitals. In particular, we show that the correlation effects lead to the momentum-dependent hybridization between different orbitals, resulting in the splitting and shifting of the flat part of the Ni-dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{z}^{2}}$$\\end{document} band. This strong renormalization of the electronic spectral function drives the charge density wave instability that is related to the intraband Ni-dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{z}^{2}}$$\\end{document} correlations. Instead, the magnetic instability stems from the Ni-dx2−y2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${d}_{{x}^{2}-{y}^{2}}$$\\end{document} orbital, which remains half-filled through the redistribution of the electronic density between different bands even upon hole doping. Consequently, the strength of the magnetic fluctuations remains nearly unchanged for the considered doping levels. We argue that this renormalization is not inherent to the stoichiometric case but can be induced by hole doping.

Gapless Neutron Superfluidity Can Explain the Late Time Cooling of Transiently Accreting Neutron Stars.

The current interpretation of the observed late time cooling of transiently accreting neutron stars in low-mass x-ray binaries during quiescence requires the suppression of neutron superfluidity in their crust at variance with recent abinitio many-body calculations of dense matter. Focusing on the two emblematic sources KS 1731-260 and MXB 1659-29, we show that their thermal evolution can be naturally explained by considering the existence of a neutron superflow driven by the pinning of quantized vortices. Under such circumstances, we find that the neutron superfluid can be in a gapless state in which the specific heat is dramatically increased compared to that in the classical BCS state assumed so far, thus delaying the thermal relaxation of the crust. We perform neutron-star cooling simulations taking into account gapless superfluidity, and we obtain excellent fits to the data, thus reconciling astrophysical observations with microscopic theories. The imprint of gapless superfluidity on other observable phenomena is briefly discussed.