On the effective reconstruction of expectation values from ab initio quantum embedding

Abstract

Quantum embedding is an appealing route to fragment a large interacting quantum system into several smaller auxiliary `cluster' problems to exploit the locality of the correlated physics. In this work we critically review approaches to recombine these fragmented solutions in order to compute non-local expectation values, including the total energy. Starting from the democratic partitioning of expectation values used in density matrix embedding theory, we motivate and develop a number of alternative approaches, numerically demonstrating their efficiency and improved accuracy as a function of increasing cluster size for both energetics and non-local two-body observables in molecular and solid state systems. These approaches consider the $N$-representability of the resulting expectation values via an implicit global wave~function across the clusters, as well as the importance of including contributions to expectation values spanning multiple fragments simultaneously, thereby alleviating the fundamental locality approximation of the embedding. We clearly demonstrate the value of these introduced functionals for reliable extraction of observables and robust and systematic convergence as the cluster size increases, allowing for significantly smaller clusters to be used for a desired accuracy compared to traditional approaches in ab initio wave~function quantum embedding.

20 pages

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• ByteQC: GPU-Accelerated Quantum Chemistry Package for Large-Scale Systems
• Fragment quantum embedding using the Householder transformation: a multi-state extension based on ensembles
• Unitary transformations within density matrix embedding approaches: A novel perspective on the self-consistent scheme for electronic structure calculation
• Local Potential Functional Embedding Theory of Molecular Systems: Localized Orbital-Based Embedding from an Exact Density-Functional Perspective
• Ab Initio Many Body Quantum Embedding and Local Correlation in Crystalline Materials using Interpolative Separable Density Fitting
• Simple Fermionic backflow states via a systematically improvable tensor decomposition