Quantum Embedding Research Articles

A static quantum embedding scheme based on coupled cluster theory.

We develop a static quantum embedding scheme that utilizes different levels of approximations to coupled cluster (CC) theory for an active fragment region and its environment. To reduce the computational cost, we solve the local fragment problem using a high-level CC method and address the environment problem with a lower-level Møller-Plesset (MP) perturbative method. This embedding approach inherits many conceptual developments from the hybrid second-order Møller-Plesset (MP2) and CC works by Nooijen [J. Chem. Phys. 111, 10815 (1999)] and Bochevarov and Sherrill [J. Chem. Phys. 122, 234110 (2005)]. We go beyond those works here by primarily targeting a specific localized fragment of a molecule and also introducing an alternative mechanism to relax the environment within this framework. We will call this approach MP-CC. We demonstrate the effectiveness of MP-CC on several potential energy curves and a set of thermochemical reaction energies, using CC with singles and doubles as the fragment solver, and MP2-like treatments of the environment. The results are substantially improved by the inclusion of orbital relaxation in the environment. Using localized bonds as the active fragment, we also report results for N=N bond breaking in azomethane and for the central C-C bond torsion in butadiene. We find that when the fragment Hilbert space size remains fixed (e.g., when determined by an intrinsic atomic orbital approach), the method achieves comparable accuracy with both a small and a large basis set. Additionally, our results indicate that increasing the fragment Hilbert space size systematically enhances the accuracy of observables, approaching the precision of the full CC solver.

Quantized embedding approaches for collective strong coupling-Connecting abinitio and macroscopic QED to simple models in polaritonics.

Collective light-matter interactions have been used to control chemistry and energy transfer, yet accessible approaches that combine abinitio methodology with large many-body quantum optical systems are missing due to the fast increase in computational cost for explicit simulations. We introduce an accessible abinitio quantum embedding concept for many-body quantum optical systems that allows us to treat the collective coupling of molecular many-body systems effectively in the spirit of macroscopic quantum electrodynamics while keeping the rigor of abinitio quantum chemistry for the molecular structure. Our approach fully includes the quantum fluctuations of the polaritonic field and yet remains much simpler and more intuitive than complex embedding approaches such as dynamical mean-field theory. We illustrate the underlying assumptions by comparison to the Tavis-Cummings model. The intuitive application of the quantized embedding approach and its transparent limitations offer a practical framework for the field of abinitio polaritonic chemistry to describe collective effects in realistic molecular ensembles.

Implementation of frozen density embedding in CP2K and OpenMolcas: CASSCF wavefunctions embedded in a Gaussian and plane wave DFT environment.

Most chemical processes happen at a local scale where only a subset of molecular orbitals is directly involved and only a subset of covalent bonds may be rearranged. To model such reactions, Density Functional Theory (DFT) is often inadequate, and the use of computationally more expensive correlated wavefunction (WF) methods is required for accurate results. Mixed-resolution approaches backed by quantum embedding theory have been used extensively to approach this imbalance. Based on the frozen density embedding freeze-and-thaw algorithm, we describe an approach to embed complete active space self-consistent field simulations run in the OpenMolcas code in a DFT environment calculated in CP2K without requiring any external tools. This makes it possible to study a local, active part of a chemical system in a larger and relatively static environment with a computational cost balanced between the accuracy of a WF method and the efficiency of DFT, which we test on environment-subsystem pairs. Finally, we apply the implementation to an oxygen molecule leaving an aluminum (111) surface and a ruthenium(IV) oxide (110) surface.

Superconductivity and Mott Physics in Organic Charge Transfer Materials.

The phase diagrams of quasi two-dimensional organic superconductors display a plethora of fundamental phenomena associated with strong electron correlations, such as unconventional superconductivity, metal-insulator transitions, frustrated magnetism and spin liquid behavior. We analyze a minimal model for these compounds, the Hubbard model on an anisotropic triangular lattice, using cutting-edge quantum embedding methods respecting the lattice symmetry. We demonstrate the existence of unconventional superconductivity by directly entering the symmetry-broken phase. We show that the crossover from the Fermi liquid metal to the Mott insulator is associated with the formation of a pseudogap. The predicted momentum-selective destruction of the Fermi surface into hot and cold regions provides motivation for further spectroscopic studies. Our theoretical results agree with experimental phase diagrams of κ-BEDT organics.

Fragment quantum embedding using the Householder transformation: A multi-state extension based on ensembles

In recent studies by Yalouz et al. [J. Chem. Phys. 157, 214112 (2022)] and Sekaran et al. [Phys. Rev. B 104, 035121 (2021) and Computation 10, 45 (2022)], density matrix embedding theory (DMET) has been reformulated through the use of the Householder transformation as a novel tool to embed a fragment within extended systems. The transformation was applied to a reference non-interacting one-electron reduced density matrix to construct fragments’ bath orbitals, which are crucial for subsequent ground state calculations. In the present work, we expand upon these previous developments and extend the utilization of the Householder transformation to the description of multiple electronic states, including ground and excited states. Based on an ensemble noninteracting density matrix, we demonstrate the feasibility of achieving exact fragment embedding through successive Householder transformations, resulting in a larger set of bath orbitals. We analytically prove that the number of additional bath orbitals scales directly with the number of fractionally occupied natural orbitals in the reference ensemble density matrix. A connection with the regular DMET bath construction is also made. Then, we illustrate the use of this ensemble embedding tool in single-shot DMET calculations to describe both ground and first excited states in a Hubbard lattice model and an ab initio hydrogen system. Finally, we discuss avenues for enhancing ensemble embedding through self-consistency and explore potential future directions.

Quantum embedding method with transformer neural network quantum states for strongly correlated materials

The neural-network quantum states (NNQS) method is rapidly emerging as a powerful tool in quantum mechanisms. While significant advancements have been achieved in simulating simple molecules using NNQS, the ab initio simulation of complex solid-state materials remains challenging. Here in this work, we have adopted the periodic density matrix embedding theory to extend the NNQS method to deal with complex solid-state systems. Our approach notably reduces the computational problem size while maintaining high accuracy. We have validated the accuracy and efficiency of our method against traditional methodologies and experimental data in extended systems, and have investigated the magnetic ordering and charge density wave state in transition metal compounds. The findings from our research indicate that the integration of quantum embedding with intuitive chemical fragmentation can significantly enhance the NNQS simulation of realistic materials.

How Well Can Quantum Embedding Method Predict the Reaction Profiles for Hydrogenation of Small Li Clusters?

Quantum computing leverages the principles of quantum mechanics in novel ways to tackle complex chemistry problems that cannot be accurately addressed using traditional quantum chemistry methods. However, the high computational cost and available number of physical qubits with high fidelity limit its application to small chemical systems. This work employed a quantum-classical framework which features a quantum active space-embedding approach to perform simulations of chemical reactions that require up to 14 qubits. This framework was applied to prototypical example metal hydrogenation reactions: the coupling between hydrogen and Li2, Li3, and Li4 clusters. Particular attention was paid to the computation of barriers and reaction energies. The predicted reaction profiles compare well with advanced classical quantum chemistry methods, demonstrating the potential of the quantum embedding algorithm to map out reaction profiles of realistic gas-phase chemical reactions to ascertain qualitative energetic trends. Additionally, the predicted potential energy curves provide a benchmark to compare against both current and future quantum embedding approaches.

Accelerating Density Matrix Embedding with Stochastic Density Fitting Theory: An Application to Hydrogen Bonded Clusters.

In this work, we demonstrate how using semistochastic density fitting (ss-DF) can accelerate self-consistent density matrix embedding theory (DMET) calculations by reducing the number of auxiliary orbitals in the three-indexed DF integrals. This reduction results in significant time savings when building the Hartree-Fock (HF) Coulomb and Exchange Matrices and in transforming integrals from the atomic orbital (AO) basis to the embedding orbital (EO) basis. We apply ss-DF to a range of hydrogen-bonded clusters to showcase its effectiveness. First, we examine how the amount of deterministic space impacts the quality of the calculation in a (H2O)10 cluster. Next, we test the computational efficiency of ss-DF compared to deterministic DF (d-DF) in water clusters containing 6-30 water molecules using a triple-ζ basis set. Finally, we perform numerical structural optimizations on water and hydrogen fluoride clusters, revealing that DMET can recover weak interactions using a back-transformed energy formula. This work demonstrates the potential of using stochastic resolution of identity in quantum embedding theories and highlights its capability to recover weak interactions effectively.

Tensor network influence functionals in the continuous-time limit: Connections to quantum embedding, bath discretization, and higher-order time propagation

Tensor network influence functionals in the continuous-time limit: Connections to quantum embedding, bath discretization, and higher-order time propagation

Quantum circuits for discrete graphical models

Graphical models are useful tools for describing structured high-dimensional probability distributions. The development of efficient algorithms for generating samples thereof remains an active research topic. In this work, we provide a quantum algorithm that enables the generation of unbiased and independent samples from general discrete graphical models. To this end, we identify a coherent embedding of the graphical model based on a repeat-until-success sampling scheme which clearly identifies whether a drawn sample represents the underlying distribution. Furthermore, we show that the success probability for finding a valid sample can be lower bounded with a quantity that depends on the number of maximal cliques and the model parameter norm. Moreover, we rigorously proof that the quantum embedding conserves the key property of graphical models, i.e., factorization over the cliques of the underlying conditional independence structure. The quantum sampling algorithm also allows for maximum likelihood learning as well as maximum a posteriori state approximation for the graphical model. Finally, the proposed quantum method shows potential to realize interesting problems on near-term quantum processors. In fact, illustrative experiments demonstrate that our method can carry out sampling and parameter learning not only with idealized simulations of quantum computers but also on actual quantum hardware solely supported by simple readout error mitigation.

Recurrent quantum embedding neural network and its application in vulnerability detection

In recent years, deep learning has been widely used in vulnerability detection with remarkable results. These studies often apply natural language processing (NLP) technologies due to the natural similarity between code and language. Since NLP usually consumes a lot of computing resources, its combination with quantum computing is becoming a valuable research direction. In this paper, we present a Recurrent Quantum Embedding Neural Network (RQENN) for vulnerability detection. It aims to reduce the memory consumption of classical models for vulnerability detection tasks and improve the performance of quantum natural language processing (QNLP) methods. We show that the performance of RQENN achieves the above goals. Compared with the classic model, the space complexity of each stage of its execution is exponentially reduced, and the number of parameters used and the number of bits consumed are significantly reduced. Compared with other QNLP methods, RQENN uses fewer qubit resources and achieves a 15.7% higher accuracy in vulnerability detection.

Quantum metric learning with fuzzy-informed learning

By constructing a quantum circuit with adjustable parameters, variational quantum circuits are capable of embedding input data into Hilbert space and facilitating the execution of complex deep learning tasks. Recently, a method known as quantum metric learning has emerged. It adaptively adjusts quantum embedding circuits to enable clusters of classical data from different categories to form linear separations in Hilbert space. This approach combines the advantages of kernel methods and is implementable on near-term quantum devices. However, applying quantum metric learning to more complex data presents challenges, largely due to the inherent fuzziness, uncertainty, and noise in the data itself and in the classical neural network preprocessing. To address these challenges, this paper proposes a fuzzy information-driven framework for quantum metric learning. This framework leverages fuzzy learning to accurately describe the uncertainty of data characteristics and adaptively integrates features, fuzziness, and uncertainty. Numerical experiments demonstrate that, compared to standard quantum metric learning, this framework achieves competitive performance and promising results. Furthermore, the interpretability provided by fuzzy logic aids in understanding the intrinsic mechanisms of the selected features during the quantum feature mapping process, offering new perspectives and approaches for better utilization of current quantum information processors.

Scalable semidefinite programming approach to variational embedding for quantum many-body problems

In quantum embedding theories, a quantum many-body system is divided into localized clusters of sites which are treated with an accurate ‘high-level’ theory and glued together self-consistently by a less accurate ‘low-level’ theory at the global scale. The recently introduced variational embedding approach for quantum many-body problems combines the insights of semidefinite relaxation and quantum embedding theory to provide a lower bound on the ground-state energy that improves as the cluster size is increased. The variational embedding method is formulated as a semidefinite program (SDP), which can suffer from poor computational scaling when treated with black-box solvers. We exploit the interpretation of this SDP as an embedding method to develop an algorithm which alternates parallelizable local updates of the high-level quantities with updates that enforce the low-level global constraints. Moreover, we show how translation invariance in lattice systems can be exploited to reduce the complexity of projecting a key matrix to the positive semidefinite cone.

Development of analytic gradients for the Huzinaga quantum embedding method and its applications to large-scale hybrid and double hybrid DFT forces.

The theory of analytic gradients is presented for the projector-based density functional theory (DFT) embedding approach utilizing the Huzinaga-equation. The advantages of the Huzinaga-equation-based formulation are demonstrated. In particular, it is shown that the projector employed does not appear in the Lagrangian, and the potential risk of numerical problems is avoided at the evaluation of the gradients. The efficient implementation of the analytic gradient theory is presented for approaches where hybrid DFT, second-order Møller-Plesset perturbation theory, or double hybrid DFT are embedded in lower-level DFT environments. To demonstrate the applicability of the method and to gain insight into its accuracy, it is applied to equilibrium geometry optimizations, transition state searches, and potential energy surface scans. Our results show that bond lengths and angles converge rapidly with the size of the embedded system. While providing structural parameters close to high-level quality for the embedded atoms, the embedding approach has the potential to relax the coordinates of the environment as well. Our demonstrations on a 171-atom zeolite and a 570-atom protein system show that the Huzinaga-equation-based embedding can accelerate (double) hybrid gradient computations by an order of magnitude with sufficient active regions and enables affordable force evaluations or geometry optimizations for molecules of hundreds of atoms.

Rigorous Screened Interactions for Realistic Correlated Electron Systems.

We derive a widely applicable first-principles approach for determining two-body, static effective interactions for low-energy Hamiltonians with quantitative accuracy. The algebraic construction rigorously conserves all instantaneous two-point correlation functions in a chosen model space at the level of the random phase approximation, improving upon the traditional uncontrolled static approximations. Applied to screened interactions within a quantum embedding framework, we demonstrate these faithfully describe the relaxation of local subspaces via downfolding high-energy physics in molecular systems, as well as enabling a systematically improvable description of the long-range plasmonic contributions in extended graphene.

Optical Properties of Defects in Solids via Quantum Embedding with Good Active Space Orbitals

Optical Properties of Defects in Solids via Quantum Embedding with Good Active Space Orbitals

Integrating subsystem embedding subalgebras and coupled cluster Green’s function: a theoretical foundation for quantum embedding in excitation manifold

In this study, we introduce a novel approach to coupled-cluster Green’s function (CCGF) embedding by seamlessly integrating conventional CCGF theory with the state-of-the-art sub-system embedding sub-algebras coupled cluster (SES-CC) formalism. This integration focuses primarily on delineating the characteristics of the sub-system and the corresponding segments of the Green’s function, defined explicitly by active orbitals. Crucially, our work involves the adaptation of the SES-CC paradigm, addressing the left eigenvalue problem through a distinct form of Hamiltonian similarity transformation. This advancement not only facilitates a comprehensive representation of the interaction between the embedded sub-system and its surrounding environment but also paves the way for the quantum mechanical description of multiple embedded domains, particularly by employing the emergent quantum flow algorithms. Our theoretical underpinnings further set the stage for a generalization to multiple embedded sub-systems. This expansion holds significant promise for the exploration and application of non-equilibrium quantum systems, enhancing the understanding of system–environment interactions. In doing so, the research underscores the potential of SES-CC embedding within the realm of quantum computations and multi-scale simulations, promising a good balance between accuracy and computational efficiency.

Subsystem density‐functional theory (update)

AbstractThe past years since the publication of our review on subsystem density‐functional theory (sDFT) (WIREs Comput Mol Sci. 2014, 4:325–362) have witnessed a rapid development and diversification of quantum mechanical fragmentation and embedding approaches related to sDFT and frozen‐density embedding (FDE). In this follow‐up article, we provide an update addressing formal and algorithmic work on sDFT/FDE, novel approximations developed for treating the non‐additive kinetic energy in these DFT/DFT hybrid methods, new areas of application and extensions to properties previously not accessible, projection‐based techniques as an alternative to solely density‐based embedding, progress in wavefunction‐in‐DFT embedding, new fragmentation strategies in the context of DFT which are technically or conceptually similar to sDFT, and the blurring boundary between advanced DFT/MM and approximate DFT/DFT embedding methods.This article is categorized under: Electronic Structure Theory > Density Functional Theory

Layerwise Quantum Deep Reinforcement Learning for Joint Optimization of UAV Trajectory and Resource Allocation

This study proposes a layerwise quantum-based deep reinforcement learning (LQ-DRL) method for optimizing continuous large space and time series problems using deep layer training. The actions in LQ-DRL are optimized using a layerwise quantum embedding that leverages the advantages of quantum computing to maximize reward and reduce training loss. Moreover, this study employs a local loss to minimize the occurrence of barren plateaus phenomena and further enhance performance. As a particular case, the proposed scheme is employed to jointly optimize: (1) UAV trajectory planning, (2) user grouping, and (3) power allocation for higher energy efficiency of a UAV as the reward. The combination of these optimized factors is referred to as action space in the presented LQ-DRL. The LQ-DRL is employed to solve the optimization problem due to its non-convexity, continuous and large action space, and time-series domain. In a practical view, LQ-DRL aims to solve the issue of energy consumption related to limited-battery energy of a UAV base station while maintaining quality-of-service (QoS) for users, by gaining maximum energy efficiency as the reward. One of real applications, as an example, LQ-DRL can be employed to maximize the energy efficiency of a UAV base station in UAV empowered disaster recovery networks scenario. The quantum circuits of layerwise quantum embedding are presented to show the practical implementation in noisy intermediate-scale quantum computers. Based on the results, LQ-DRL outperformed the classical DRL by achieving higher effective dimension, rewards, and lower learning losses. In addition, better performances were achieved using more layers.

Short-term photovoltaic power forecasting based on hybrid quantum gated recurrent unit

Photovoltaic power generation forecasting is crucial for energy management, smart grid construction, and energy markets. This study proposes a hybrid quantum–classical gated recurrent unit (HQGRU)-based framework for forecasting short-term photovoltaic power generation in a time-series manner. The HQGRU model uses a classical layer followed by a quantum embedding circuit to convert classical data into quantum data. Subsequently, variational quantum circuits are used for feature extraction. To demonstrate the performance of the proposed model, we used practical data on photovoltaic power generation and the weather in Busan, Republic of Korea. The results demonstrate the high accuracy of the proposed HQGRU model.