Orbital entanglement and correlation from pCCD-tailored Coupled Cluster wave functions

Abstract: Wave functions based on electron-pair states provide inexpensive and reliable models to describe quantum many-body problems containing strongly-correlated electrons, given that broken-pair states have been appropriately accounted for by, for instance, a posteriori corrections. In this article, we analyse the performance of electron-pair methods in predicting orbital-based correlation spectra. We focus on the (orbital-optimized) pair-coupled cluster Doubles (pCCD) ansatz with a linearized coupled-cluster (LCC) correction. Specifically, we scrutinize how orbital-based entanglement and correlation measures can be determined from a pCCD-tailored CC wave function. Furthermore, we employ the single-orbital entropy, the orbital-pair mutual information, and the eigenvalue spectra of the two-orbital reduced density matrices to benchmark the performance of the LCC correction for the one-dimensional Hubbard model with periodic boundary condition as well as the N$_2$ and F$_2$ molecules against DMRG reference calculations. Our study indicates that pCCD-LCC accurately reproduces the orbital-pair correlation patterns in the weak-correlation limit and for molecules close to their equilibrium structure. Hence, we can conclude that pCCD-LCC predicts reliable wave functions in this regime. In the strong-correlation limit and for molecules with stretched bonds, the LCC correction, generally, overestimates orbital-pair correlations.