Accuracy of two-particle N -representability conditions for describing different spin states and the singlet-triplet gap in the linear acene series


Variational two-electron reduced-density-matrix (2-RDM) methods can provide a reference-independent description of the electronic structure of strongly correlated molecules and materials. These methods represent one of few ways of performing large active-space-based computations that are beyond the scope of conventional configuration-interaction-based approaches. However, implementations of the method are quite rare, making it difficult for the quantum chemistry community to assess the utility of the approach. Here, we discuss an open-shell implementation of the variational 2-RDM method and explore its ability to describe different spin states in several model systems, including linear hydrogen chains and linear acenes. The largest calculations considered are comparable to complete-active-space computations with 50 electrons in 50 orbitals.

Publication Title

Molecular Physics