Bootstrap Embedding for Molecules in Extended Basis Sets
Henry K. Tran, Leah P. Weisburn, Minsik Cho, Shaun Weatherly, Hong‐Zhou Ye, Troy Van Voorhis
Abstract
Quantum embedding methods are powerful tools to exploit the locality of electron correlation, but thus far many wave function-in-wave function methods have focused on small (e.g., minimal) basis sets. One major challenge for extended basis sets lies in defining consistent atom- or fragment-localized orbitals in spite of the larger spatial extent of the underlying atomic orbitals. In this work, we modify a particular form of quantum embedding, bootstrap embedding (BE), to the case of extended basis sets. We find that using intrinsic atomic orbital (IAO) localization schemes alongside BE converges to ∼99.7% of the CCSD correlation energy in 3-21G, 6-311G, and cc-pVDZ basis sets for reasonably sized fragments. These results mark an important first step in extending the success of embedding methods to properly studying dynamic correlation.