Accuracy of projected atomic virtual orbital space in embedding applications

22 April 2024, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


The performance of the recently suggested projected atomic orbitals (PAO) approach as the virtual space in excited state projection-based embedding applications is analyzed. The role of the parameters in the PAO generation is discussed and the impact of different choices is evaluated on the ground state of the stacked formaldehyde and pyrrole dimers. A comparison of excitation energies obtained with PAOs and localized virtual orbitals is given and the role of diffuse basis functions is discussed using a benchmark set from previous studies.


excited states
intermolecular interaction
virtual orbitals
projected atomic orbitals

Supplementary materials

Supplemental material: Accuracy of projected atomic virtual orbital space in embedding applications
Supplementary material includes details of the electronic structure calculations, structures of formaldehyde and the Pyrrol complexes, details of the PCE calculations, all excitation energies for the XH-27 benchmark set, and difference density natural orbital plots of the first four Rydberg states of the Uracil.5H2O complex, as obtained from the supersystem EOM-CCSD calculation, as well as the eigenvalues of PAO overlap matrix


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