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

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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.
Original languageEnglish
JournalJournal of Chemical Theory and Computation
Publication statusAccepted/In press - 15 Mar 2023


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