One-body Reduced Density Matrix Research Articles

Frozen Natural Orbitals for the State-Averaged Driven Similarity Renormalization Group.

We present a reduced-cost implementation of the state-averaged driven similarity renormalization group (SA-DSRG) based on the frozen natural orbital (FNO) approach. The natural orbitals (NOs) are obtained by diagonalizing the one-body reduced density matrix from SA-DSRG second-order perturbation theory (SA-DSRG-PT2). We consider three criteria to truncate the virtual NOs for the subsequent electron correlation treatment beyond SA-DSRG-PT2. An additive second-order correction is applied to the SA-DSRG Hamiltonian to reintroduce correlation effects from the discarded orbitals. The FNO SA-DSRG method is benchmarked on 35 small organic molecules in the QUEST database. When keeping 98-99% of the cumulative occupation numbers, the mean absolute error in the vertical transition energies due to FNO is less than 0.01 eV. Using the same FNO threshold, we observe a speedup of 9 times compared to the conventional SA-DSRG implementation for nickel carbonyl with a quadruple-ζ basis set. The FNO approach enables nonperturbative SA-DSRG computations on chloroiron corrole [FeCl(C19H11N4)] with more than 1000 basis functions, surpassing the current limit of a conventional implementation.

Exploiting the Hessian for a Better Convergence of the SCF-RDMFT Procedure.

One-body reduced density matrix functional theory provides an alternative to density functional theory, which is able to treat static correlation while keeping a relatively low computation scaling. Its disadvantageous cost comes mainly from a slow convergence of the self-consistent energy optimization. To improve on that problem, we propose in this work the use of the Hessian of the energy, including the coupling term. We show that using the exact Hessian is very effective at reducing the number of iterations. However, since the exact Hessian is too expensive to use in practice, we propose an approximation based on an inexpensive exact part and BFGS updates.

Extracting many-body quantum resources within one-body reduced density matrix functional theory

Extracting many-body quantum resources within one-body reduced density matrix functional theory

The convexity condition of density-functional theory.

It has long been postulated that within density-functional theory (DFT), the total energy of a finite electronic system is convex with respect to electron count so that 2Ev[N0] ≤ Ev[N0 - 1] + Ev[N0 + 1]. Using the infinite-separation-limit technique, this Communication proves the convexity condition for any formulation of DFT that is (1) exact for all v-representable densities, (2) size-consistent, and (3) translationally invariant. An analogous result is also proven for one-body reduced density matrix functional theory. While there are known DFT formulations in which the ground state is not always accessible, indicating that convexity does not hold in such cases, this proof, nonetheless, confirms a stringent constraint on the exact exchange-correlation functional. We also provide sufficient conditions for convexity in approximate DFT, which could aid in the development of density-functional approximations. This result lifts a standing assumption in the proof of the piecewise linearity condition with respect to electron count, which has proven central to understanding the Kohn-Sham bandgap and the exchange-correlation derivative discontinuity of DFT.

A Versatile Unitary Transformation Framework for an Optimal Bath Construction in Density-Matrix Based Quantum Embedding Approaches

The performance of embedding methods is directly tied to the quality of the bath orbital construction. In this paper, we develop a versatile framework, enabling the investigation of the optimal construction of the orbitals of the bath. As of today, in state-of-the-art embedding methods, the orbitals of the bath are constructed by performing a Singular Value Decomposition (SVD) on the impurity-environment part of the one-body reduced density matrix, as originally presented in Density Matrix Embedding Theory. Recently, the equivalence between the SVD protocol and the use of unitary transformation, the so-called Block-Householder transformation, has been established. We present a generalization of the Block-Householder transformation by introducing additional flexible parameters. The additional parameters are optimized such that the bath-orbitals fulfill physically motivated constraints. The efficiency of the approach is discussed and exemplified in the context of the half-filled Hubbard model in one-dimension.

Self-consistent optimization of the trial wave function within the constrained path auxiliary field quantum Monte Carlo method using mixed estimators

We propose a scheme to implement the self-consistent optimization of the trial wave function within the constrained path auxiliary field quantum Monte Carlo (CP-AFQMC) method in the framework of natural orbitals. In this scheme, a new trial wave function in the form of a Slater determinant is constructed from the CP-AFQMC results by diagonalizing the mixed estimator of the one-body reduced density matrix. We compare two ways (from real and mixed estimators in CP-AFQMC) to calculate the one-body reduced density matrix in the self-consistent process and study the ground state of a doped two-dimensional Hubbard model to test the accuracy of the two schemes. By comparing the local density, occupancy, and ground state energy we find the scheme in which a one-body reduced density matrix is calculated from the mixed estimator is computationally more efficient and provides more accurate results with less fluctuation. The local densities from the mixed estimator scheme agree well with the numerically exact values. This scheme provides a useful tool for studying strongly correlated electron systems.

Tailoring dynamical fermionization: Delta-kick cooling of a Tonks-Girardeau gas

In one spatial dimension, quantum exchange statistics and interactions are inextricably intertwined. As a manifestation, the expansion dynamics of a Tonks-Girardeau gas is characterized by dynamical fermionization (DF), whereby the momentum distribution approaches that of a spin-polarized Fermi gas. Using a phase-space analysis and the unitary evolution of the one-body reduced density matrix, we show that DF can be tailored and reversed, using a generalization of delta kick cooling (DKC) to interacting systems, establishing a simple protocol to rescale the initial momentum distribution. The protocol applies to both expansions and compressions and can be used for microscopy of quantum correlations.

Quantum embedding of multi-orbital fragments using the block-Householder transformation.

Recently, some of the authors introduced the use of the Householder transformation as a simple and intuitive method for embedding local molecular fragments [see Sekaran et al., Phys. Rev. B 104, 035121 (2021) and Sekaran et al., Computation 10, 45 (2022)]. In this work, we present an extension of this approach to the more general case of multi-orbital fragments using the block version of the Householder transformation applied to the one-body reduced density matrix, unlocking the applicability to general quantum chemistry/condensed matter physics Hamiltonians. A step-by-step construction of the block Householder transformation is presented. Both physical and numerical areas of interest of the approach are highlighted. The specific mean-field (noninteracting) case is thoroughly detailed as it is shown that the embedding of a given N spin-orbital fragment leads to the generation of two separated sub-systems: (1) a 2N spin-orbitals "fragment+bath" cluster that exactly contains N electrons and (2) a remaining cluster's "environment" described by so-called core electrons. We illustrate the use of this transformation in different cases of embedding scheme for practical applications. We particularly focus on the extension of the previously introduced Local Potential Functional Embedding Theory and Householder-transformed Density Matrix Functional Embedding Theory to the case of multi-orbital fragments. These calculations are realized on different types of systems, such as model Hamiltonians (Hubbard rings) and ab initio molecular systems (hydrogen rings).

Entanglement and seniority

Background: In quantum mechanics, entanglement is the most striking phenomenon which has no counterpart in classical systems. Although different approaches have already been developed to study correlations in the case of indistinguishable particles, the exploration of the so-called mode entanglement is still in its initial stage in nuclear physics.Purpose: We aim to study mode entanglement in the seniority model, derive analytic formulas for the one-body reduced density matrix of states with seniority $\ensuremath{\nu}=0,\phantom{\rule{0.16em}{0ex}}1,\phantom{\rule{0.16em}{0ex}}2$, and 3, and also determine the particle number dependence of the one-body reduced density matrix for arbitrary seniority. In addition, we compare the predictions of the seniority model with the results of the shell model to gain insight into the structure and correlations of the ground and lowest yrast states.Methods: In the seniority model the analytic results are calculated using the quasispin formalism. The numerical shell model calculations are carried out in the standard shell model framework using an inert core. The applied realistic effective interactions are derived earlier using the $G$-matrix formalism. The density matrix renormalization group method is also applied in order to directly calculate the mode entropies.Results: In the seniority model simple analytical expressions are given for the mode entropies. The peculiar behavior of the half-filled shells and the seniority-zero states is revealed. Numerical results are presented for the lightest stable calcium isotopes and for $^{94}\mathrm{Ru}$ nucleus.Conclusions: For $^{94}\mathrm{Ru}$, the seniority model accounts for the $0{g}_{9/2}$ mode entropies, but seniority mixing is important for certain yrast states. Interaction induced quantum fluctuations decrease the occupation of the $0{f}_{5/2}$, $1{p}_{3/2}$, and $1{p}_{1/2}$ shells, and result in non-negligible mode entropies on these shells, too, clearly outside the scope of the simple ${(0{g}_{9/2})}^{4}$ seniority model. The $0{f}_{7/2}$ shell based seniority model is more accurate for the $\mathrm{Ca}$ isotopes, but seniority mixing is substantial for some $^{44}\mathrm{Ca}$ yrast states, too. Mode and one-body entanglement entropies are useful tools to investigate the structure of quantum correlations in nuclei.

Quench dynamics of two interacting atoms in a one-dimensional anharmonic trap

A temporal response of two interacting particles to a quench of the coupling strength in one-dimensional harmonic and anharmonic traps is explored. The coupling strength is changed from repulsive to attractive interactions and vice versa. The time evolution of the fidelity, wave packet, one-body reduced density matrix and momentum distributions is analyzed in details. It was found that impacts of the pre- and postquench states interchange during the dynamics. In the case of the anharmonic trap additional contribution of the center-of-mass excited states comes into play and the whole evolution becomes significantly altered. Yet the impact of the pre- and postquench states in some cases still could be identified. The quench dynamics of the ground and excited states are considered.

A reduced cost four-component relativistic coupled cluster method based on natural spinors.

We present the theory, implementation, and benchmark results for a frozen natural spinors based reduced cost four-component relativistic coupled cluster method. The natural spinors are obtained by diagonalizing the one-body reduced density matrix from a relativistic second-order Møller-Plesset calculation based on a four-component Dirac-Coulomb Hamiltonian. The correlation energy in the coupled cluster method converges more rapidly with respect to the size of the virtual space in the frozen natural spinor basis than that observed in the standard canonical spinors obtained from the Dirac-Hartree-Fock calculation. The convergence of properties is not smooth in the frozen natural spinor basis. However, the inclusion of the perturbative correction smoothens the convergence of the properties with respect to the size of the virtual space in the frozen natural spinor basis and greatly reduces the truncation errors in both energy and property calculations. The accuracy of the frozen natural spinor based coupled cluster methods can be controlled by a single threshold and is a black box to use.

Machine learning universal bosonic functionals

The one-body reduced density matrix $\gamma$ plays a fundamental role in describing and predicting quantum features of bosonic systems, such as Bose-Einstein condensation. The recently proposed reduced density matrix functional theory for bosonic ground states establishes the existence of a universal functional $\mathcal{F}[\gamma]$ that recovers quantum correlations exactly. Based on a novel decomposition of $\gamma$, we have developed a method to design reliable approximations for such universal functionals: our results suggest that for translational invariant systems the constrained search approach of functional theories can be transformed into an unconstrained problem through a parametrization of an Euclidian space. This simplification of the search approach allows us to use standard machine-learning methods to perform a quite efficient computation of both $\mathcal{F}[\gamma]$ and its functional derivative. For the Bose-Hubbard model, we present a comparison between our approach and Quantum Monte Carlo.

Decomposition of the Electronic Energy in Terms of Density, Density Coherence, and the Connected Part of the Two-Body Reduced Density Matrix.

We analyzed static and dynamic electron correlation by decomposing the total electronic energy of calculations by restricted Hartree-Fock theory, complete active-space self-consistent field (CASSCF) theory, and multireference configuration interaction (MRCI). We used three different schemes to break down the relative energy contributions to the potential energy curves for the dissociation of H2, F2, and N2. The first decomposition scheme involves the classical and nonclassical components of the energy. The second and third recognize the part of the energy that is not expressible in terms of the one-body reduced density matrix; this is called the connected energy. The unconnected component is further decomposed into a part calculable from the density and the part calculable from the density coherence. The first decomposition scheme shows that the sum of the one-electron energy and the classical two-electron energy contains a negligible portion of the static correlation. This quantity has a relatively small variance between the three levels, especially for CASSCF and MRCI. This provides an explanation of why multiconfiguration pair-density functional theory and multiconfiguration density-coherence functional theory are able to improve the CASSCF energy. The latter two decompositions show that the connected energy contains a significant portion of static correlation. The energy representable by either the density or the density coherence is significantly different at the three levels. Mixing the density and density coherence between different methods may lead to a systematic error in the bond dissociation energy and the equilibrium bond distance, indicating that the density energy component and the density coherence energy component both include a significant amount of both static and dynamic correlation. These wave function decompositions can be useful for developing new functionals for density functional theory, density-coherence functional theory, density matrix functional theory, and pair-density functional theory and for guiding expectations for these theories.

Implications of the unitary invariance and symmetry restrictions on the development of proper approximate one-body reduced-density-matrix functionals

In many of the approximate functionals in one-body reduced density matrix (1RDM) functional theory, the approximate two-body reduced density matrix (2RDM) in the natural orbital representation only depends on the natural occupation numbers. In Phys. Rev. A 92, 012520 (2015) Wang and Knowles initialised a discussion of to what extent this simplification is valid, by introducing two different H$_4$ geometries with identical natural occupation numbers, but different 2RDMs. Gritsenko has argued that this feature is due symmetry [Phys. Rev. A 97, 026501 (2018)]. This work aims to contribute to the discussion on the following points: 1) one should rather speak of symmetry-restricted variants of the universal functional, than saying that the universal functional is symmetry dependent; 2) the unitary invariance of degenerate NOs can lead to large deviations in the 2RDM elements, especially the phase of the NOs; 3) symmetry-restricted functionals are constructed for the H$_4$ geometries considered by Wang and Knowles, whose structure could serve as guide in the construction of approximate 1RDM functionals.

MCTDH-X: The multiconfigurational time-dependent Hartree method for indistinguishable particles software

We introduce and describe the multiconfigurational time-depenent Hartree for indistinguishable particles (MCTDH-X) software, which is hosted, documented, and distributed at http://ultracold.org. This powerful tool allows the investigation of ground state properties and dynamics of interacting quantum many-body systems in different spatial dimensions. The MCTDH-X software is a set of programs and scripts to compute, analyze, and visualize solutions for the time-dependent and time-independent many-body Schrödinger equation for indistinguishable quantum particles. As the MCTDH-X software represents a general solver for the Schrödinger equation, it is applicable to a wide range of problems in the fields of atomic, optical, molecular physics, and condensed matter systems. In particular, it can be used to study light–matter interactions, correlated dynamics of electrons in the solid state as well as some aspects related to quantum information and computing. The MCTDH-X software solves a set of nonlinear coupled working equations based on the application of the time-dependent variational principle to the Schrödinger equation. These equations are obtained by using an ansatz for the many-body wavefunction that is a expansion in a set of time-dependent, fully symmetrized bosonic (X = B) or fully anti-symmetrized fermionic (X = F) many-body basis states. It is the time-dependence of the basis set that enables MCTDH-X to deal with quantum dynamics at a superior accuracy as compared to, for instance, exact diagonalization approaches with a static basis, where the number of basis states necessary to capture the dynamics of the wavefunction typically grows rapidly with time. Herein, we give an introduction to the MCTDH-X software via an easy-to-follow tutorial with a focus on accessibility. The illustrated exemplary problems are hosted at http://ultracold.org/tutorial and consider the physics of a few interacting bosons or fermions in a double-well potential. We explore computationally the position-space and momentum-space density, the one-body reduced density matrix, Glauber correlation functions, phases, (dynamical) phase transitions, and the imaging of the quantum systems in single-shot images. Although a few particles in a double well potential represent a minimal model system, we are able to demonstrate a rich variety of phenomena with it. We use the double well to illustrate the fermionization of bosonic particles, the crystallization of fermionic particles, characteristics of the superfluid and Mott-insulator quantum phases in Hubbard models, and even dynamical phase transitions. We provide a complete set of input files and scripts to redo all computations in this paper at http://ultracold.org/data/tutorial_input_files.zip, accompanied by tutorial videos at https://tinyurl.com/tjx35sq. Our tutorial should guide the potential users to apply the MCTDH-X software also to more complex systems.

Insights into one-body density matrices using deep learning.

The one-body reduced density matrix (1-RDM) of a many-body system at zero temperature gives direct access to many observables, such as the charge density, kinetic energy and occupation numbers. It would be desirable to express it as a simple functional of the density or of other local observables, but to date satisfactory approximations have not yet been found. Deep learning is the state of the art approach to performing high dimensional regressions and classification tasks, and is becoming widely used in the condensed matter community to develop increasingly accurate density functionals. Autoencoders are deep learning models that perform efficient dimensionality reduction, allowing the distillation of data to the fundamental features needed to represent it. By training autoencoders on a large data-set of 1-RDMs from exactly solvable real-space model systems, and performing principal component analysis, the machine learns to what extent the data can be compressed and hence how it is constrained. We gain insight into these machine learned constraints and employ them to inform approximations to the 1-RDM as a functional of the charge density. We exploit known physical properties of the 1-RDM in the simplest possible cases to perform feature engineering, where we inform the structure of the models from known mathematical relations, allowing us to integrate existing understanding into the machine learning methods. By comparing various deep learning approaches we gain insight into what physical features of the density matrix are most amenable to machine learning, utilising both known and learned characteristics.

Fidelity and Entropy Production in Quench Dynamics of Interacting Bosons in an Optical Lattice

We investigate the dynamics of a few bosons in an optical lattice induced by a quantum quench of a parameter of the many-body Hamiltonian. The evolution of the many-body wave function is obtained by solving the time-dependent many-body Schrödinger equation numerically, using the multiconfigurational time-dependent Hartree method for bosons (MCTDHB). We report the time evolution of three key quantities, namely, the occupations of the natural orbitals, that is, the eigenvalues of the one-body reduced density matrix, the many-body Shannon information entropy, and the quantum fidelity for a wide range of interactions. Our key motivation is to characterize relaxation processes where various observables of an isolated and interacting quantum many-body system dynamically converge to equilibrium values via the quantum fidelity and via the production of many-body entropy. The interaction, as a parameter, can induce a phase transition in the ground state of the system from a superfluid (SF) state to a Mott-insulator (MI) state. We show that, for a quench to a weak interaction, the fidelity remains close to unity and the entropy exhibits oscillations. Whereas for a quench to strong interactions (SF to MI transition), the relaxation process is characterized by the first collapse of the quantum fidelity and entropy saturation to an equilibrium value. The dip and the non-analytic nature of quantum fidelity is a hallmark of dynamical quantum phase transitions. We quantify the characteristic time at which the quantum fidelity collapses and the entropy saturates.

Principal Domains in Local Correlation Theory.

The computational efficiency of local correlation methods is strongly dependent on the size of the domain of functions used to expand local correlating orbitals such as orbital specific or pair natural orbitals. Here, we define a principal domain of order m as the subset of m one-particle functions that provides the best support for a given n-electron wave function by maximizing the partial trace of the one-body reduced density matrix. Principal domains maximize the overlap between the wave function and its approximant for two-electron systems and are the domain selection equivalent of Löwdin's natural orbitals. We present an efficient linear scaling greedy algorithm for obtaining principal domains of projected atomic orbitals and demonstrate its utility in the context of the pair natural orbital local correlation theory. We numerically determine thresholds such that the projected atomic orbital domain error is an order of magnitude smaller than the pair natural orbital truncation error.

Reduced density matrix functional theory for superconductors

We present an \textit{ab initio} theory for superconductors, based on a unique mapping between the statistical density operator at equilibrium, on the one hand, and the corresponding one-body reduced density matrix $\gamma$ and the anomalous density $\chi$, on the other. This new formalism for superconductivity yields the existence of a universal functional $\mathfrak{F}_\beta[\gamma,\chi]$ for the superconductor ground state, whose unique properties we derive. We then prove the existence of a Kohn-Sham system at finite temperature and derive the corresponding Bogoliubov-de Gennes-like single particle equations. By adapting the decoupling approximation from density functional theory for superconductors we bring these equations into a computationally feasible form. Finally, we use the existence of the Kohn-Sham system to extend the Sham-Schl\"uter connection and derive a first exchange-correlation functional for our theory. This reduced density matrix functional theory for superconductors has the potential of overcoming some of the shortcomings and fundamental limitations of density functional theory of superconductivity.

Correlations of strongly interacting one-dimensional ultracold dipolar few-boson systems in optical lattices

Strongly interacting finite ensembles of dipolar bosons in commensurately filled one-dimensional optical lattices exhibit diverse quantum phases that are rich in physics. As the strength of the long-range boson–boson interaction increases, the system transitions across different phases: from a superfluid, through a Mott-insulator and a Tonks–Girardeau gas to a crystal state. The signature of these phases and their transitions can be unequivocally identified by an experimentally detectable order parameter, recently described in Phys. Rev. A 98 235301 (2018 []). Herein, we calculate the momentum distributions and the normalized Glauber correlation functions of dipolar bosons in a one-dimensional optical lattice in order to characterize all their phases. To understand the behavior of the correlations across the phase transitions, we first investigate the eigenfunctions and eigenvalues of the one-body reduced density matrix as a function of the dipolar interaction strength. We then analyze the real- and momentum-space Glauber correlation functions, thereby gaining a spatially and momentum-resolved insight into the coherence properties of these quantum phases. We find an intriguing structure of non-local correlations that, independently of other observables, reveal the phase transitions of the system. In particular, spatial localization and momentum delocalization accompany the formation of correlated islands in the density as interactions become stronger. Our study showcases that precise control of intersite correlations is possible through the manipulation of the depth of the lattice, while intrasite correlations can be influenced by changing the dipolar interaction strength.