Quantum embedding based on the (one-electron-reduced) density matrix is revisited by means of the unitary Householder transformation. While being exact and equivalent to (but formally simpler than) density matrix embedding theory (DMET) in the noninteracting case, the resulting Householder-transformed density matrix functional embedding theory (Ht-DMFET) preserves, by construction, the single-particle character of the bath when electron correlation is introduced. In Ht-DMFET, the projected “$\mathrm{impurity}+\mathrm{bath}$” cluster's Hamiltonian (from which approximate local properties of the interacting lattice can be extracted) becomes an explicit functional of the density matrix. In the spirit of single-impurity DMET, we consider in this work a closed (two-electron) cluster constructed from the full-size noninteracting density matrix. When the (Householder-transformed) interaction on the bath site is taken into account, per-site energies obtained for the half-filled one-dimensional Hubbard lattice match almost perfectly the exact Bethe ansatz results in all correlation regimes. In the strongly correlated regime, the results deteriorate away from half-filling. This can be related to the electron number fluctuations in the (two-site) cluster which are neither described in Ht-DMFET nor in regular DMET. As expected, the per-site energies dramatically improve when increasing the number of embedded impurities. Formal connections with density/density matrix functional theories have been briefly discussed and should be explored further. Work is currently in progress in this direction.

The equivalence in one-electron quantum baths between the practical implementation of density matrix embedding theory (DMET) and the more recent Householder-transformed density matrix functional embedding theory has been shown previously in the standard but special case where the reference full-size (one-electron reduced) density matrix, from which the bath is constructed, is idempotent [S. Yalouz et al., J. Chem. Phys. 157, 214112 (2022)]. We prove mathematically that the equivalence remains valid when the density matrix is not idempotent anymore, thus allowing for the construction of correlated (one-electron) quantum baths. A density-matrix functional exactification of DMET is derived within the present unified quantum embedding formalism. Numerical examples reveal that the embedding cluster can be quite sensitive to the level of density-matrix functional approximation used for computing the reference density matrix.

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).

Quantum embedding is a divide and conquer strategy that aims at solving the electronic Schrödinger equation of sizeable molecules or extended systems. We establish in the present work a clearer and in-principle-exact connection between density matrix embedding theory (DMET) and density-functional theory (DFT) within the simple but nontrivial one-dimensional Hubbard model. For that purpose, we use our recent reformulation of single-impurity DMET as a Householder transformed density-matrix functional embedding theory (Ht-DMFET). On the basis of well-identified density-functional approximations, a self-consistent local potential functional embedding theory (LPFET) is formulated and implemented. Combining both LPFET and DMET numerical results with our formally exact density-functional embedding theory reveals that a single statically embedded impurity can in principle describe the density-driven Mott–Hubbard transition, provided that a complementary density-functional correlation potential (which is neglected in both DMET and LPFET) exhibits a derivative discontinuity (DD) at half filling. The extension of LPFET to multiple impurities (which would enable to circumvent the modeling of DDs) and its generalization to quantum chemical Hamiltonians are left for future work.

Penser l'imbrication quantique des électrons fortement corrélés en théorie de la fonctionnelle de la (matrice) densité: L'objectif de cette thèse est le développement et l'implémentation de nouvelles méthodes dites d'embedding à l'intersection entre la chimie et la physique. Afin de pourvoir une description précise des molécules et matériaux fortement corrélés, l'embedding quantique sera appliqué au modèle d'Hubbard et généralisé à des Hamil­tonien moléculaires Ab initio. Nous vérifierons si la density matrix embedding the­ory (DMET) peut être rendu formellement exacte et améliorée tout en préservant la nature orbitalaire de notre partitionnement quantique. Plus précisément, nous réécrirons notre approche d'embedding comme étant une fonctionnelle de la matrice densité à un corps, contournant ainsi la décomposition de Schmidt de la fonction d'onde de référence ( corrélée ou non) décrivant le système dans son intégralité. En­fin, nous clarifierons les parallèles entre la DMET et les théories en principe exactes que sont la density functional theory (DFT) et la reduced density matrix functional theory (RDMFT). Sur cette base, plusieurs alternatives de la DMET seront ex­plorées.