Influence Of The N-Representability Conditions On The Variational Determination Of Two-Electron Reduced Density Matrices For Ground And Excited N-Electron States In The Doubly-Occupied Configuration Interaction Space

D. CORVALAN; O.B. OÑA; D.R. ALCOBA; A. TORRE; L. LAIN; G.E. MASSACCESI

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Lugar: New York; Año: 2022 vol. 157 p. 204103 - 204103

0021-9606

In this work, we analyze the effectiveness of different sets of well-known necessary N-representability conditions that are imposed on the variational determination of two-electron reduced density matrices corresponding to the ground and excited states of N-electron Hamiltonians, within doubly-occupied configuration interaction subspaces. The two-electron reduced density matrix elements are determined so that they are suitably related to those of higher order reduced density matrices and other associated matrices, up to a given order, constituting positive semidefinite matrices. These conditions up to 2-, 3-, and 4-order have been sequentially imposed on the variational calculation of the expectation values of the dispersion operator corresponding to several Hamiltonian models, obtaining the electronic spectra. These results have been contrasted with those arising from the full configuration interaction method, illuminating the sufficiency/insufficiency of the variational N-representability conditions applied.