The simulation of non-equil. electron dynamics in real systems provides a challenge for theor. methods due to the need to treat both large system sizes and electron correlation. Towards this goal, we present an extension of the d. matrix embedding theory (DMET) for the simulation of real-time electron dynamics in strongly correlated systems. As in the previously developed static DMET, real-time DMET partitions the system into an impurity corresponding the region of interest coupled to the surrounding environment, which is efficiently represented by a quantum bath of the same size as the impurity. The dynamics of the coupled impurity and bath embedding problem are obtained through use of the time-dependent variational principle. The methodol. allows for the efficient and accurate simulation of non-equil. electron dynamics in the presence of strong correlation, reaching total system sizes unobtainable by conventional methodol.
The simulation of non-equil. electron dynamics in real systems provides a challenge for theor. methods due to the need to treat both large system sizes and electron correlation. Towards this goal, we present an extension of the d. matrix embedding theory (DMET) for the simulation of real-time electron dynamics in strongly correlated systems. As in the previously developed static DMET, real-time DMET partitions the system into an impurity corresponding the region of interest coupled to the surrounding environment, which is efficiently represented by a quantum bath of the same size as the impurity. The dynamics of the coupled impurity and bath embedding problem are obtained through use of the time-dependent variational principle. The methodol. allows for the efficient and accurate simulation of non-equil. electron dynamics in the presence of strong correlation, reaching total system sizes unobtainable by conventional methodol.
In this work, we derive a multi-fragment real-time extension of the projected density matrix embedding theory (pDMET) designed to treat non-equilibrium electron dynamics in strongly correlated systems. As in the previously developed static pDMET, the real time pDMET partitions the total system into many fragments; the coupling between each fragment and the rest of the system is treated through a compact representation of the environment in terms of a quantum bath. The real-time pDMET involves simultaneously propagating the wavefunctions for each separate fragment-bath embedding system along with an auxiliary mean-field wavefunction of the total system. The equations of motion are derived by (i) projecting the time-dependent Schrödinger equation in the fragment and bath space associated with each separate fragment and by (ii) enforcing the pDMET matching conditions between the global 1-particle reduced density matrix (1-RDM) obtained from the fragment calculations and the mean-field 1-RDM at all points in time. The accuracy of the method is benchmarked through comparisons to time-dependent density-matrix renormalization group and time-dependent Hartree-Fock (TDHF) theory; the methods were applied to a one- and two-dimensional single-impurity Anderson model and multi-impurity Anderson models with ordered and disordered distributions of the impurities. The results demonstrate a large improvement over TDHF and rapid convergence to the exact dynamics with an increase in fragment size. Our results demonstrate that the real-time pDMET is a promising and flexible method that balances accuracy and efficiency to simulate the non-equilibrium electron dynamics in heterogeneous systems of large size.
We introduce real-time density matrix embedding theory (DMET), a dynamical quantum embedding theory for computing non-equilibrium electron dynamics in strongly correlated systems. As in the previously developed static DMET, real-time DMET partitions the system into an impurity corresponding to the region of interest coupled to the surrounding environment, which is efficiently represented by a quantum bath of the same size as the impurity. In this work, we focus on a simplified single-impurity time-dependent formulation as a first step toward a multi-impurity theory. The equations of motion of the coupled impurity and bath embedding problem are derived using the time-dependent variational principle. The accuracy of real-time DMET is compared to that of time-dependent complete active space self-consistent field (TD-CASSCF) theory and time-dependent Hartree-Fock (TDHF) theory for a variety of quantum quenches in the single impurity Anderson model (SIAM), in which the Hamiltonian is suddenly changed (quenched) to induce a non-equilibrium state. Real-time DMET shows a marked improvement over the mean-field TDHF, converging to the exact answer even in the non-trivial Kondo regime of the SIAM. However, as expected from analogous behavior in static DMET, the constrained structure of the real-time DMET wavefunction leads to a slower convergence with respect to active space size, in the single-impurity formulation, relative to TD-CASSCF. Our initial results suggest that real-time DMET provides a promising framework to simulate non-equilibrium electron dynamics in which strong electron correlation plays an important role, and lays the groundwork for future multi-impurity formulations.
We extend our density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] from lattice models to the full chemical Hamiltonian. DMET allows the many-body embedding of arbitrary fragments of a quantum system, even when such fragments are open systems and strongly coupled to their environment (e.g., by covalent bonds). In DMET, empirical approaches to strong coupling, such as link atoms or boundary regions, are replaced by a small, rigorous quantum bath designed to reproduce the entanglement between a fragment and its environment. We describe the theory and demonstrate its feasibility in strongly correlated hydrogen ring and grid models; these are not only beyond the scope of traditional embeddings but even challenge conventional quantum chemistry methods themselves. We find that DMET correctly describes the notoriously difficult symmetric dissociation of a 4 × 3 hydrogen atom grid, even when the treated fragments are as small as single hydrogen atoms. We expect that DMET will open up new ways of treating complex strongly coupled, strongly correlated systems in terms of their individual fragments.
Density matrix embedding theory (DMET) has emerged as a powerful tool for performing wave function-in-wave function embedding for strongly correlated systems. In traditional DMET, an accurate calculation is performed on a small impurity embedded in a mean field bath. Here, we extend the original DMET equations to account for correlation in the bath via an antisymmetrized geminal power (AGP) wave function. The resulting formalism has a number of advantages. First, it allows one to properly treat the weak correlation limit of independent pairs, which DMET is unable to do with a mean-field bath. Second, it associates a size extensive correlation energy with a given density matrix (for the models tested), which AGP by itself is incapable of providing. Third, it provides a reasonable description of charge redistribution in strongly correlated but non-periodic systems. Thus, AGP-DMET appears to be a good starting point for describing electron correlation in molecules, which are aperiodic and possess both strong and weak electron correlation.
Quantum embedding methods enable the study of large, strongly correlated quantum systems by (usually self-consistent) decomposition into computationally manageable subproblems, in the spirit of divide-and-conquer methods. Among these, Density Matrix Embedding Theory (DMET) is an efficient approach that enforces self-consistency at the level of one-particle reduced density matrices (1-RDMs), facilitating applications across diverse quantum systems. However, conventional DMET is constrained by the requirement that the global 1-RDM (low-level descriptor) be an orthogonal projector, limiting flexibility in bath construction and potentially impeding accuracy in strongly correlated regimes. In this work, we introduce a generalized DMET framework in which the low-level descriptor can be an arbitrary 1-RDM and the bath construction is based on optimizing a quantitative criterion related to the maximal disentanglement between different fragments. This yields an alternative yet controllable bath space construction for generic 1-RDMs, lifting a key limitation of conventional DMET. We demonstrate its consistency with conventional DMET in appropriate limits and exploring its implications for bath construction, downfolding (impurity Hamiltonian construction), low-level solvers, and adaptive fragmentation. We expect that this more flexible framework, which leads to several new variants of DMET, can improve the robustness and accuracy of DMET.
We introduce density matrix embedding theory (DMET), a quantum embedding theory for computing frequency-independent quantities, such as ground-state properties, of infinite systems. Like dynamical mean-field theory, DMET maps the bulk interacting system to a simpler impurity model and is exact in the noninteracting and atomic limits. Unlike dynamical mean-field theory, DMET is formulated in terms of the frequency-independent local density matrix, rather than the local Green's function. In addition, it features a finite, algebraically constructible bath of only one bath site per impurity site, with no bath discretization error. Frequency independence and the minimal bath make DMET a computationally simple and efficient method. We test the theory in the one-dimensional and two-dimensional Hubbard models at and away from half filling, and we find that compared to benchmark data, total energies, correlation functions, and metal-insulator transitions are well reproduced, at a tiny computational cost.