Wavefunction optimization at the complete basis set limit with Multiwavelets and DMRG

Abstract: The density matrix renormalization group (DMRG) is a powerful numerical technique to solve strongly correlated quantum systems: it deals well with systems which are not dominated by a single configuration (unlike Coupled Cluster) and it converges rapidly to the Full Configuration Interaction (FCI) limit (unlike truncated Configuration Interaction (CI) expansions). In this work, we develop an algorithm integrating DMRG within the multiwavelet-based multiresolution analysis (MRA). Unlike fixed basis sets, multiwavelets offer an adaptive and hierarchical representation of functions, approaching the complete basis set limit to a specified precision. As a result, this combined technique leverages the multireference capability of DMRG and the complete basis set limit of MRA and multiwavelets. More specifically, we adopt a pre-existing Lagrangian optimization algorithm for orbitals represented in the MRA domain and improve its computational efficiency by replacing the original CI calculations with DMRG. Additionally, we substitute the reduced density matrices computation with the direct extraction of energy gradients from the DMRG tensors. We apply our method to small systems such H2, He, HeH2, BeH2 and N2. The results demonstrate that our approach reduces the final energy while keeping the number of orbitals low compared to FCI calculations on an atomic orbital basis set.