Generalization of the Tensor Product Selected CI Method for Molecular Excited States.

Abstract

In a recent paper [JCTC, 2020, 16, 6098], we introduced a new approach for accurately approximating full CI ground states in large electronic active-spaces called Tensor Product Selected CI (TPSCI). In TPSCI, a large orbital active space is first partitioned into disjoint sets (clusters) for which the exact, local many-body eigenstates are obtained. Tensor products of these locally correlated many-body states are taken as the basis for the full, global Hilbert space. By folding correlation into the basis states themselves, the low-energy eigenstates become increasingly sparse, creating a more compact selected CI expansion. While we demonstrated that this approach can improve accuracy for a variety of systems, there is even greater potential for applications to excited states, particularly those which have some excited-state character. In this paper, we report on the accuracy of TPSCI for excited states, including a far more efficient implementation in the Julia programming language. In traditional SCI methods that use a Slater determinant basis, accurate excitation energies are obtained only after a linear extrapolation and at a large computational cost. We find that TPSCI with perturbative corrections provides accurate excitation energies for several excited states of various polycyclic aromatic hydrocarbons with respect to the extrapolated result (i.e., near exact result). Further, we use TPSCI to report highly accurate estimates of the lowest 31 eigenstates for a tetracene tetramer system with an active space of 40 electrons in 40 orbitals, giving direct access to the initial bright states and the resulting 18 doubly excited (biexcitonic) states.