Excited-State Spectra of Strongly Correlated Molecules from a Reduced-Density-Matrix Approach

Excited-state energies are computed in the space of single-electron transitions from the ground state from only a knowledge of the two-electron reduced density matrix (2-RDM). Previous work developed and applied the theory to small molecular systems with accurate results, but applications to both larger and more correlated molecules were hindered by ill-conditioning of the effective eigenvalue problem. Here we improve the excited-spectra 2-RDM theory through a stable Hamiltonian-shifted regularization algorithm that removes the near singularities within the computation. The theory with ground-state 2-RDMs from the variational 2-RDM method is applied to the excited energies of strongly correlated molecules including the optical band gap of hydrogen and acene chains, the singlet–triplet splitting of nickel dithiolates, as well as the low-lying excited states of an optical dye. While single-excitation theories like CISD and TD-DFT underestimate band gaps and excited-state splittings, the 2-RDM theory yields ...