Modeling core-level excitations with variationally optimized reduced-density matrices and the extended random phase approximation.

Abstract

The information contained within ground-state one- and two-electron reduced-density matrices (RDMs) can be used to compute wave functions and energies for electronically excited states through the extended random phase approximation (ERPA). The ERPA is an appealing framework for describing excitations out of states obtained via the variational optimization of the two-electron RDM (2-RDM), as the variational 2-RDM (v2RDM) approach itself can only be used to describe the lowest-energy state of a given spin symmetry. The utility of the ERPA for predicting near-edge features relevant to x-ray absorption spectroscopy is assessed for the case that the 2-RDM is obtained from a ground-state v2RDM-driven complete active space self-consistent field (CASSCF) computation. A class of killer conditions for the CASSCF-specific ERPA excitation operator is derived, and it is demonstrated that a reliable description of core-level excitations requires an excitation operator that fulfills these conditions; the core-valence separation (CVS) scheme yields such an operator. Absolute excitation energies evaluated within the CASSCF/CVS-ERPA framework are slightly more accurate than those obtained from the usual random phase approximation (RPA), but the CVS-ERPA is not more accurate than RPA for predicting the relative positions of near-edge features. Nonetheless, CVS-ERPA is established as a reasonable starting point for the treatment of core-level excitations using variationally optimized 2-RDMs.