Selected non-orthogonal configuration interaction with compressed single and double excitations

Abstract

Addressing both dynamic and static correlation accurately is a primary goal in electronic structure theory. Non-orthogonal configuration interaction (NOCI) is a versatile tool for treating static correlation, offering chemical insights by combining diverse reference states. Nevertheless, achieving quantitative accuracy requires the inclusion of missing dynamic correlation. This work introduces a framework for compressing orthogonal single and double excitations into an NOCI of a much smaller dimension. This compression is repeated with each Slater determinant in a reference NOCI, resulting in another NOCI that includes all its single and double excitations (NOCISD), effectively recovering the missing dynamic correlations from the reference. This compressed NOCISD is further refined through a selection process using metric and energy tests (SNOCISD). We validate the effectiveness of SNOCISD through its application to the dissociation of the nitrogen molecule and the hole-doped two-dimensional Hubbard model at various interaction strengths.