Linear Response Selected Configuration Interaction

Abstract

In this work, we extend selected configuration interaction (SCI) methods beyond energies and expectation values by introducing a linear response (LR) framework for molecular response properties. Existing SCI approaches are capable of approximating the energy of the full configuration interaction (FCI) wave function with high accuracy but at a much lower cost. However, conventional determinant selection will, by design, mainly select determinants that are expected to improve energies, and this can lead to the omission of many determinants that are important for wave function response. We address this by introducing two new selection criteria motivated by linear response theory. Using these extended determinant selection criteria, we demonstrate that LR-SCI can systematically converge toward the FCI limit for static polarizabilities. Using a damped LR formulation, we compute the water K-edge X-ray absorption spectrum in active spaces up to (10e, 58o). Finally, we use LR-SCI to compute NMR spin-spin coupling constants for water, where we find that accuracy beyond that offered by CCSDT can be achieved. Overall, LR-SCI offers a promising route to compute response properties with near-FCI accuracy to systems beyond the reach of exact FCI.