One-particle Density Research Articles

Multifractality and Fock-space localization in many-body localized states: One-particle density matrix perspective

Many-body localization (MBL) is well characterized in Fock space. To quantify the degree of this Fock-space localization, the multifractal dimension ${D}_{q}$ is employed; it has been claimed that ${D}_{q}$ shows a jump from the delocalized value ${D}_{q}=1$ in the eigenstate thermalization hypothesis (ETH) phase to a smaller value $0<{D}_{q}<1$ at the ETH-MBL transition, yet exhibiting a conspicuous discrepancy from the fully localized value ${D}_{q}=0$, which indicates that multifractality remains inside the MBL phase. Here, to better quantify the situation, we employ, instead of the commonly used computational basis, the one-particle density matrix (OPDM) and use its eigenstates (natural orbitals) as a Fock state basis for representing many-body eigenstates $|\ensuremath{\psi}\ensuremath{\rangle}$ of the system. Using this basis, we compute ${D}_{q}$ and other indices quantifying the Fock-space localization, such as the local purity $S$, which is derived from the occupation spectrum ${{n}_{\ensuremath{\alpha}}}$ (eigenvalues of the OPDM). We highlight the statistical distribution of Hamming distance ${x}_{\ensuremath{\mu}\ensuremath{\nu}}$ occurring in the pairwise coefficients $|{a}_{\ensuremath{\mu}}{|}^{2}{|{a}_{\ensuremath{\nu}}|}^{2}$ in $S$, and compare this with a related quantity considered in the literature.

The orbital picture of the first dipole hyperpolarizability from many-body response theory.

We present an approach for obtaining a molecular orbital picture of the first dipole hyperpolarizability (β) from correlated many-body electronic structure methods. Ab initio calculations of β rely on quadratic response theory, which recasts the sum-over-all-states expression of β into a closed-form expression by calculating a handful of first- and second-order response states; for resonantly enhanced β, damped response theory is used. These response states are then used to construct second-order response reduced one-particle density matrices (1PDMs), which, upon visualization in terms of natural orbitals (NOs), facilitate a rigorous and black-box mapping of the underlying electronic structure with β. We explain the interpretation of different components of the response 1PDMs and the corresponding NOs within both the undamped and damped response theory framework. We illustrate the utility of this new tool by deconstructing β for cis-difluoroethene, para-nitroaniline, and hemibonded OH· + H2O complex, computed within the framework of coupled-cluster singles and doubles response theory, in terms of the underlying response 1PDMs and NOs for a range of frequencies.

Lewis Structures from Open Quantum Systems Natural Orbitals: Real Space Adaptive Natural Density Partitioning.

Building chemical models from state-of-the-art electronic structure calculations is not an easy task, since the high-dimensional information contained in the wave function needs to be compressed and read in terms of the accepted chemical language. We have already shown (Phys. Chem. Chem. Phys.2018, 20, 2136830095829) how to access Lewis structures from general wave functions in real space by reformulating the adaptive natural density partitioning (AdNDP) method proposed by Zubarev and Boldyrev (Phys. Chem. Chem. Phys.2008, 10, 520718728862). This provides intuitive Lewis descriptions from fully orbital invariant position space descriptors but depends on not immediately accessible higher order cumulant density matrices. By using an open quantum systems (OQS) perspective, we here show that the rigorously defined OQS fragment natural orbitals can be used to build a consistent real space adaptive natural density partitioning based only on spatial information and the system’s one-particle density matrix. We show that this rs-AdNDP approach is a cheap, efficient, and robust technique that immerses electron counting arguments fully in the real space realm.

Multiconfiguration Density-Coherence Functional Theory.

This paper presents a new theory called multiconfiguration density coherence functional theory (MC-DCFT). This theory provides a new route to define density functionals for multiconfiguration wave functions, in particular by using the one-particle density matrix in the coordinate representation. The theory is illustrated by calculating the dissociation curve of four heteronuclear and homonuclear diatomic molecules, namely, H2, F2, N2, and HF, using density coherence functionals converted from PBE, BLYP, and PW91. By introducing two parameters in the converted density functionals, we are able to calculate bond dissociation energies of comparable accuracy as those calculated by multiconfiguration pair-density functional theory (MC-PDFT) and complete active space second-order perturbation theory (CASPT2). This demonstrates that it would be possible to build a successful multiconfiguration density functional theory based on density coherence.

Lifshitz tails at spectral edge and holography with a finite cutoff

We propose the holographic description of the Lifshitz tail typical for one-particle spectral density of bounded disordered system in D = 1 space. To this aim the “polymer representation” of the Jackiw-Teitelboim (JT) 2D dilaton gravity at a finite cutoff is used and the corresponding partition function is considered as the weighted sum over paths of fixed length in an external magnetic field. We identify the regime of small loops, responsible for emergence of a Lifshitz tail in the Gaussian disorder, and relate the strength of disorder to the boundary value of the dilaton. The geometry corresponding to the Poisson disorder in the boundary theory involves random paths fluctuating in the vicinity of the hard impenetrable cut-off disc in a 2D plane. It is shown that the ensemble of “stretched” paths evading the disc possesses the Kardar-Parisi-Zhang (KPZ) scaling for fluctuations, which is the key property that ensures the dual description of the Lifshitz tail in the spectral density for the Poisson disorder.

On the Spectrum of the One-Particle Density Matrix

The one-particle density matrix $$\gamma(x, y)$$ is one of the key objects in quantum-mechanical approximation schemes. The self-adjoint operator $$\Gamma$$ with kernel $$\gamma(x, y)$$ is trace class, but no sharp results on the decay of its eigenvalues were previously known. The note presents the asymptotic formula $$\lambda_k \sim (Ak)^{-8/3}$$ , $$A \ge 0$$ , as $$k\to\infty$$ for the eigenvalues $$\lambda_k$$ of the operator $$\Gamma$$ and describes the main ideas of the proof.

A Comparison of Three Ways to Measure Time-Dependent Densities With Quantum Simulators

Quantum algorithms are touted as a way around some classically intractable problems such as the simulation of quantum mechanics. At the end of all quantum algorithms is a quantum measurement whereby classical data is extracted and utilized. In fact, many of the modern hybrid-classical approaches are essentially quantum measurements of states with short quantum circuit descriptions. Here, we compare and examine three methods of extracting the time-dependent one-particle probability density from a quantum simulation: direct Z-measurement, Bayesian phase estimation, and harmonic inversion. We have tested these methods in the context of the potential inversion problem of time-dependent density functional theory. Our test results suggest that direct measurement is the preferable method. We also highlight areas where the other two methods may be useful and report on tests using Rigetti's quantum virtual device. This study provides a starting point for imminent applications of quantum computing.

Equation-of-motion coupled-cluster method with double electron-attaching operators: Theory, implementation, and benchmarks.

We report a production-level implementation of the equation-of-motion (EOM) coupled-cluster (CC) method with double electron-attaching (DEA) EOM operators of 2p and 3p1h types, EOM-DEA-CCSD. This ansatz, suitable for treating electronic structure patterns that can be described as two-electrons-in-many orbitals, represents a useful addition to the EOM-CC family of methods. We analyze the performance of EOM-DEA-CCSD for energy differences and molecular properties. By considering reduced quantities, such as state and transition one-particle density matrices, we compare EOM-DEA-CCSD wave functions with wave functions computed by other EOM-CCSD methods. The benchmarks illustrate that EOM-DEA-CCSD is capable of treating diradicals, bond-breaking, and some types of conical intersections.

Quench Dynamics of the Ideal Bose Polaron at Zero and Nonzero Temperatures

We give a detailed account of a stationary impurity in an ideal Bose-Einstein condensate, which we call the ideal Bose polaron, at both zero and non-zero temperatures and arbitrary strength of the impurity-boson coupling. The time evolution is solved exactly and it is found that, surprisingly, many of the features that have been predicted for the real BEC are already present in this simpler setting and can be understood analytically therein. We obtain explicit formulae for the time evolution of the condensate wave function at $T=0$ and of the one-particle density matrix at $T>0$. For negative scattering length, the system is found to thermalize even though the dynamics are perfectly coherent. The time evolution and thermal values of the Tan contact are derived and compared to a recent experiment. We find that contrary to the Fermi polaron, the contact is not bounded at unitarity as long as a condensate exists. An explicit formula for the dynamical overlap at $T=0$ allows us to compute the rf spectrum which can be understood in detail by relating it to the two-body problem of one boson and the impurity.

One-particle spectral densities and phase diagrams of one-dimensional proton conductors

The equilibrium states of one-dimensional proton conductors in the systems with hydrogen bonds are investigated. Our extended hard-core boson lattice model includes short-range interactions between hydrogen ions, their transfer along the hydrogen bonds with two-minima local anharmonic potential, as well as their inter-bond hopping, and the modulating field is taken into account. The exact diagonalization method for finite one-dimensional system with periodic boundary conditions is used. The existence of various phases of the system at T = 0, depending on the values of short-range interactions between particles and the modulating field strength, is established by analyzing the character of the obtained frequency dependence of one-particle spectral density; the phase diagrams are built.

A range-separated generalized Kohn-Sham method including a long-range nonlocal random phase approximation correlation potential.

Based on our recently published range-separated random phase approximation (RPA) functional [Kreppel et al., "Range-separated density-functional theory in combination with the random phase approximation: An accuracy benchmark," J. Chem. Theory Comput. 16, 2985-2994 (2020)], we introduce self-consistent minimization with respect to the one-particle density matrix. In contrast to the range-separated RPA methods presented so far, the new method includes a long-range nonlocal RPA correlation potential in the orbital optimization process, making it a full-featured variational generalized Kohn-Sham (GKS) method. The new method not only improves upon all other tested RPA schemes including the standard post-GKS range-separated RPA for the investigated test cases covering general main group thermochemistry, kinetics, and noncovalent interactions but also significantly outperforms the popular G0W0 method in estimating the ionization potentials and fundamental gaps considered in this work using the eigenvalue spectra obtained from the GKS Hamiltonian.

Solvable Model of a Generic Driven Mixture of Trapped Bose-Einstein Condensates and Properties of a Many-Boson Floquet State at the Limit of an Infinite Number of Particles.

A solvable model of a periodically driven trapped mixture of Bose–Einstein condensates, consisting of interacting bosons of mass driven by a force of amplitude and interacting bosons of mass driven by a force of amplitude , is presented. The model generalizes the harmonic-interaction model for mixtures to the time-dependent domain. The resulting many-particle ground Floquet wavefunction and quasienergy, as well as the time-dependent densities and reduced density matrices, are prescribed explicitly and analyzed at the many-body and mean-field levels of theory for finite systems and at the limit of an infinite number of particles. We prove that the time-dependent densities per particle are given at the limit of an infinite number of particles by their respective mean-field quantities, and that the time-dependent reduced one-particle and two-particle density matrices per particle of the driven mixture are condensed. Interestingly, the quasienergy per particle does not coincide with the mean-field value at this limit, unless the relative center-of-mass coordinate of the two Bose–Einstein condensates is not activated by the driving forces and . As an application, we investigate the imprinting of angular momentum and its fluctuations when steering a Bose–Einstein condensate by an interacting bosonic impurity and the resulting modes of rotations. Whereas the expectation values per particle of the angular-momentum operator for the many-body and mean-field solutions coincide at the limit of an infinite number of particles, the respective fluctuations can differ substantially. The results are analyzed in terms of the transformation properties of the angular-momentum operator under translations and boosts, and as a function of the interactions between the particles. Implications are briefly discussed.

Solitary states in the mean-field limit.

We study active matter systems where the orientational dynamics of underlying self-propelled particles obey second-order equations. By primarily concentrating on a spatially homogeneous setup for particle distribution, our analysis combines theories of active matter and oscillatory networks. For such systems, we analyze the appearance of solitary states via a homoclinic bifurcation as a mechanism of the frequency clustering. By introducing noise, we establish a stochastic version of solitary states and derive the mean-field limit described by a partial differential equation for a one-particle probability density function, which one might call the continuum Kuramoto model with inertia and noise. By studying this limit, we establish second-order phase transitions between polar order and disorder. The combination of both analytical and numerical approaches in our study demonstrates an excellent qualitative agreement between mean-field and finite-size models.

Thermal effects on the electronic properties of sodium electride under high pressures

Sodium is a simple metal at ambient conditions, while it transits to an electride phase at pressures above \ensuremath{\sim}160 GPa along the room-temperature isotherm. We explore the thermal effects on the electronic properties of the $\mathit{hP}4$ phase of sodium along the $\ensuremath{\rho}=5.872\phantom{\rule{0.16em}{0ex}}\mathrm{g}/\mathrm{c}{\mathrm{m}}^{3}$ isochore. We quantitatively classify this phase as an insulator based on the criterion of nearsightedness of the one-particle density matrix. Ab initio calculations suggest that the band gap of this insulator decreases with increasing temperature along the isochore, primarily because of ionic distortions, culminating in an insulator-to-metal transition upon melting at ${T}_{m}\ensuremath{\approx}2100\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. This transition is accompanied by residual electronic localization (in $d$ orbitals) in the form of dynamic electron bubbles and a change in hybridization from p-d to s-p upon melting. This transition is explored by tracking the electronic and electro-optical properties along the isochore under consideration.

Equation-of-Motion Coupled-Cluster Theory to Model L-Edge X-ray Absorption and Photoelectron Spectra.

We present an extension of the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) theory for computing X-ray L-edge spectra, both in the absorption (XAS) and in the photoelectron (XPS) regimes. The approach is based on the perturbative evaluation of spin-orbit couplings using the Breit-Pauli Hamiltonian and nonrelativistic wave functions described by the fc-CVS-EOM-CCSD ansatz (EOM-CCSD within the frozen-core core-valence separated (fc-CVS) scheme). The formalism is based on spinless one-particle density matrices. The approach is illustrated by modeling XAS and XPS of several model systems ranging from Ar to small molecules containing sulfur and silicon.

One-particle density matrix of a trapped Lieb–Liniger anyonic gas

We provide a thorough characterisation of the zero-temperature one-particle density matrix of trapped interacting anyonic gases in one dimension, exploiting recent advances in the field theory description of spatially inhomogeneous quantum systems. We first revisit homogeneous anyonic gases with point-wise interactions. In the harmonic Luttinger liquid expansion of the one-particle density matrix for finite interaction strength, the non-universal field amplitudes were not yet known. We extract them from the Bethe Ansatz formula for the field form factors, providing an exact asymptotic expansion of this correlation function, thus extending the available results in the Tonks–Girardeau limit. Next, we analyse trapped gases with non-trivial density profiles. By applying recent analytic and numerical techniques for inhomogeneous Luttinger liquids, we provide exact expansions for the one-particle density matrix. We present our results for different confining potentials, highlighting the main differences with respect to bosonic gases.

Constrained thermalization and topological superconductivity

We examine the thermalisation/localization trade off in an interacting and disordered Kitaev model, specifically addressing whether signatures of many-body localization can coexist with the systems topological phase. Using methods applicable to finite size systems, (e.g. the generalized one-particle density matrix, eigenstate entanglement entropy, inverse zero modes coherence length) we identify a regime of parameter space in the vicinity of the non-interacting limit where topological superconductivity survives together with a significant violation of Eigenstate-Thermalisation-Hypothesis (ETH) at finite energy-densities. We further identify an anomalous behaviour of the von Neumann entanglement entropy which can be attributed to the prethermalisation-like effects that occur due to lack of hybridization between high-energy eigenstates reflecting an approximate particle conservation law. In this regime the system tends to thermalise to a generalised Gibbs ensemble (as opposed to the grand canonical ensemble). Moderate disorder tends to drive the system towards stronger hybridization and a standard thermal ensemble, where the approximate conservation law is violated. This behaviour is cutoff by strong disorder which obstructs many body effects thus violating ETH and reducing the entanglement entropy.

Traveling bands, clouds, and vortices of chiral active matter.

We consider stochastic dynamics of self-propelled particles with nonlocal normalized alignment interactions subject to phase lag. The role of the lag is to indirectly generate chirality into particle motion. To understand large-scale behavior, we derive a continuum description of an active Brownian particle flow with macroscopic scaling in the form of a partial differential equation for a one-particle probability density function. Due to indirect chirality, we find a spatially homogeneous nonstationary analytic solution for this class of equations. Our development of kinetic and hydrodynamic theories towards such a solution reveals the existence of a wide variety of spatially nonhomogeneous patterns reminiscent of traveling bands, clouds, and vortical structures of linear active matter. Our model may thereby serve as the basis for understanding the nature of chiral active media and designing multiagent swarms with designated behavior.

A simple molecular orbital picture of RIXS distilled from many-body damped response theory.

Ab initio calculations of resonant inelastic x-ray scattering (RIXS) often rely on damped response theory, which prevents the divergence of response solutions in the resonant regime. Within the damped response theory formalism, RIXS moments are expressed as the sum over all electronic states of the system [sum-over-states (SOS) expressions]. By invoking resonance arguments, this expression can be reduced to a few terms, an approximation commonly exploited for the interpretation of computed cross sections. We present an alternative approach: a rigorous formalism for deriving a simple molecular orbital picture of the RIXS process from many-body calculations using the damped response theory. In practical implementations, the SOS expressions of RIXS moments are recast in terms of matrix elements between the zero-order wave functions and first-order frequency-dependent response wave functions of the initial and final states such that the RIXS moments can be evaluated using complex response one-particle transition density matrices (1PTDMs). Visualization of these 1PTDMs connects the RIXS process with the changes in electronic density. We demonstrate that the real and imaginary components of the response 1PTDMs can be interpreted as contributions of the undamped off-resonance and damped near-resonance SOS terms, respectively. By analyzing these 1PTDMs in terms of natural transition orbitals, we derive a rigorous, black-box mapping of the RIXS process into a molecular orbital picture. We illustrate the utility of the new tool by analyzing RIXS transitions in the OH radical, benzene, para-nitroaniline, and 4-amino-4'-nitrostilbene. These examples highlight the significance of both the near-resonance and off-resonance channels.

Many-body localization from a one-particle perspective in the disordered one-dimensional Bose-Hubbard model

We numerically investigate 1D Bose-Hubbard chains with onsite disorder by means of exact diagonalization. A primary focus of our work is on characterizing Fock-space localization in this model from the single-particle perspective. For this purpose, we compute the one-particle density matrix (OPDM) in many-body eigenstates. We show that the natural orbitals (the eigenstates of the OPDM) are extended in the ergodic phase and real-space localized when one enters into the MBL phase. Furthermore, the distributions of occupations of the natural orbitals can be used as measures of Fock-space localization in the respective basis. Consistent with previous studies, we observe signatures of a transition from the ergodic to the many-body localized (MBL) regime when increasing the disorder strength. We further demonstrate that Fock-space localization, albeit weaker, is also evidently present in the distribution of the physical densities in the MBL regime, both for soft- and hardcore bosons. Moreover, the full distribution of the densities of the physical particles provides a one-particle measure for the detection of the ergodic-MBL transition which could be directly accessed in experiments with ultra-cold gases.