Correlated electron physics is intrinsically a multiscale problem, since high-energy electronic states screen the interactions between the correlated electrons close to the Fermi level, thereby reducing the magnitude of the interaction strength and dramatically shortening its range. Thus the handling of screening is an essential ingredient in the first-principles modeling of correlated electron systems. Screening is an intrinsically dynamic process and the corresponding downfolding methods such as the constrained random phase approximation indeed produce a dynamic interaction. However, many low-energy methods require an instantaneous interaction as input, which makes it necessary to map the fully dynamic interaction to an effective instantaneous interaction strength. It is not clear if and when such an effective model can capture the physics of the one with dynamic interaction and how to best perform the mapping. Here, we provide a systematic benchmark relevant to correlated materials, in the form of the Anderson impurity model. Overall, we find that a static approximation can be valid and that the moment-based approach recently proposed by Scott and Booth can be a good tool to find the value of the static interaction. We also identify physical regimes, especially under doping, where an instantaneous interaction cannot capture all of the relevant physics.
Microscopically conserving reduced models of many-body systems have a long, highly successful history. Established perturbative theories of this type are the random-phase approximation for Coulomb fluids and the particle-particle ladder model for nuclear matter. There are also more physically comprehensive diagrammatic approximations, such as the induced-interaction and parquet models. Notwithstanding their explanatory power, some theories have lacked an explicit Hamiltonian from which all significant system properties, static and dynamic, emerge canonically. This absence can complicate evaluation of the conserving sum rules, essential consistency checks on the validity of any theory. In a series of papers Kraichnan introduced a stochastic embedding procedure to generate explicit Hamiltonians for common approximations for the full many-body problem. Existence of a Hamiltonian greatly eases the task of securing fundamental identities in such studies. I revisit Kraichnan's method to apply it to correlation theories for which such a canonical framework has been missing. I exhibit Hamiltonians for more elaborate correlated models incorporating both long-range screening and short-range scattering phenomena. These are relevant to the study of strongly interacting electrons and condensed quantum systems broadly.
We introduce extended density matrix embedding theory (EDMET), a static quantum embedding theory explicitly self-consistent with respect to local two-body physics. This overcomes the biggest practical and conceptual limitation of more traditional one-body embedding methods, namely the lack of screening and treatment of longer-range interactions. This algebraic zero-temperature embedding augments a local interacting cluster model with a minimal number of bosons from a description of the full system correlations via the random phase approximation, and admits an analytic approach to build a self-consistent Coulomb-exchange-correlation kernel. For extended Hubbard models with nonlocal interactions, this leads to the accurate description of phase transitions, static quantities, and dynamics. We also move towards ab initio systems via the Parriser-Parr-Pople model of conjugated coronene derivatives, finding good agreement with experimental optical gaps.
In a previous work [Phys. Rev. B 77, 085122 (2008)], a procedure for constructing low-energy models of electrons in solids was proposed. The procedure starts with dividing the Hilbert space into two subspaces: the low-energy part (``
d space'') and the rest of the space (``
r space''). The low-energy model is constructed for the
d space by eliminating the degrees of freedom of the
r space. The thus derived model contains the strength of electron correlation expressed by a partially screened Coulomb interaction, calculated in the constrained random-phase approximation (cRPA), where screening channels within the
d space,
Pd, are subtracted. One conceptual problem of this established downfolding method is that for entangled bands it is not clear how to cut out the
d space and how to distinguish
Pd from the total polarization. Here, we propose a simple procedure to overcome this difficulty. The
d space is defined to be an isolated set of bands generated from a set of maximally localized Wannier basis, which consequently defines
Pd. The
r subspace is constructed as the complementary space orthogonal to the
d subspace, resulting in two sets of completely disentangled bands. Using these disentangled bands, the effective parameters of the
d space are uniquely determined by the cRPA method. The method is successfully applied to
3d transition metals.
Accurate many-body treatments of condensed-phase systems are challenging because correlated solvers such as the full configuration interaction (FCI) and the density matrix renormalization group (DMRG) scale exponentially with system size. Downfolding and embedding approaches mitigate this cost but typically require prior selection of a correlated subspace, which can be difficult to determine in heterogeneous or extended systems. Here, we introduce a stochastic cluster expansion framework for efficiently recovering the total correlation energy of large systems with near-DMRG accuracy and without the need to select an active space a priori . By combining correlation contributions from randomly sampled environment orbitals with an exactly treated subspace of interest, the method reproduces total energies for nonreacting and reactive systems while drastically reducing computational cost. The approach also provides a quantitative diagnostic for molecule–solvent correlation, guiding principled embedding decisions. This framework enables systematically improvable many-body calculations in extended systems, opening the door to high-accuracy studies of chemical processes in condensed phase environments.
Recent developments in methods and computational power render it possible to realistically simulate nanoscopic systems such as surfaces, two-dimensional materials, and nanodots including strong electronic correlations. Nanoscopic structuring enables the tailoring of the electronic structure which can be the basis of future electronic devices. This thesis addresses method developments and applications at the interface of ab-initio methods and model based many-body methods for the case of nanoscopically structured systems with strong correlations. In contrast to bulk materials, low-dimensional materials exhibit long-range interactions due to reduced screening. In this work, the general question how these long-range interactions affect electronic properties is investigated. To this end, a variational approach which approximates models with long-range interactions by models with only local interactions is introduced. For the case of an ab-initio derived model of graphene it is found that nonlocal interactions stabilize the semimetallic phase. The quality of this approach is discussed using a simple test case. Realistic models of interacting impurities embedded in an extended solid involve a large amount of bath sites and low symmetries regarding the impurity, which renders an exact treatment impossible. A variational algorithm is presented which optimizes corresponding exactly solvable effective models. Thus, the method is a proposition to an unambiguous solution of the so-called bath-discretization problem in exact diagonalization approaches to the Anderson impurity model. The method is benchmarked for a simple test case and applied to realistic models of Co atoms in Cu hosts and Fe atoms on alkali surfaces. Finally, the (001) surface of Cr is investigated by incorporating local correlation effects into a material realistic description derived from density functional theory. To this end, the LDA DMFT method is used to calculate spectral functions, which are compared to spectroscopic experimental data. So far open experimental features are thereby clarified. Cr(001) exemplifies a situation where correlation effects are determined by the geometric structure of a material: While correlations effects are weak in bulk Cr, they are key for the electronic structure of the Cr(001) surface.