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Excited States by Coupling Piris Natural Orbital Functionals with the Extended Random-Phase Approximation

2024; American Chemical Society; Volume: 20; Issue: 5 Linguagem: Inglês

10.1021/acs.jctc.3c01194

1549-9626

Juan Felipe Huan Lew-Yee, Iván Alejandro Bonfil-Rivera, Mario Piris, Jorge M. del Campo,

Quantum, superfluid, helium dynamics

In this work, we explore the use of Piris natural orbital functionals (PNOFs) to calculate excited-state energies by coupling their reconstructed second-order reduced density matrix with the extended random-phase approximation (ERPA). We have named the general method PNOF-ERPA, and specific approaches are referred to as PNOF-ERPA0, PNOF-ERPA1, and PNOF-ERPA2, according to the way the excitation operator is built. The implementation has been tested in the first excited states of H2, HeH+, LiH, Li2, and N2 showing good results compared to the configuration interaction (CI) method. As expected, an increase in accuracy is observed on going from ERPA0 to ERPA1 and ERPA2. We also studied the effect of electron correlation included by PNOF5, PNOF7, and the recently proposed global NOF (GNOF) on the predicted excited states. PNOF5 appears to be good and may even provide better results in very small systems, but including more electron correlation becomes important as the system size increases, where GNOF achieves better results. Overall, the extension of PNOF to excited states has been successful, making it a promising method for further applications.