Quantum embedding of multi-orbital fragments using the block-Householder transformation.

Abstract

Recently, some of the authors introduced the use of the Householder transformation as a simple and intuitive method for embedding local molecular fragments [see Sekaran et al., Phys. Rev. B 104, 035121 (2021) and Sekaran et al., Computation 10, 45 (2022)]. In this work, we present an extension of this approach to the more general case of multi-orbital fragments using the block version of the Householder transformation applied to the one-body reduced density matrix, unlocking the applicability to general quantum chemistry/condensed matter physics Hamiltonians. A step-by-step construction of the block Householder transformation is presented. Both physical and numerical areas of interest of the approach are highlighted. The specific mean-field (noninteracting) case is thoroughly detailed as it is shown that the embedding of a given N spin-orbital fragment leads to the generation of two separated sub-systems: (1) a 2N spin-orbitals "fragment+bath" cluster that exactly contains N electrons and (2) a remaining cluster's "environment" described by so-called core electrons. We illustrate the use of this transformation in different cases of embedding scheme for practical applications. We particularly focus on the extension of the previously introduced Local Potential Functional Embedding Theory and Householder-transformed Density Matrix Functional Embedding Theory to the case of multi-orbital fragments. These calculations are realized on different types of systems, such as model Hamiltonians (Hubbard rings) and ab initio molecular systems (hydrogen rings).