We reveal limitations of several standard coupled-cluster (CC) methods with perturbation-theory based noniterative or approximate iterative treatments of triple excitations when applied to the determination of highly accurate potential energy curves (PECs) of ionic dimers, such as the XΣg+2 electronic ground state of Rb2+. Such computations are of current interest for the understanding of ion–atom interactions in the ultracold regime. We demonstrate that these CC methods lead to an unphysical long-range barrier for the Rb2+ system. The barrier is small but spoils the long-range behavior of the PEC. The effect is also found for other X2+ systems, such as X = Li, Na, and K. Calculations using a flexible framework for obtaining leading perturbative triples corrections derived using an analytic CC singles and doubles energy derivative formulation demonstrate that the origin of this problem lies in the use of T̂3 amplitudes obtained from approximate CC singles, doubles, and triples amplitude equations. It is shown that the unphysical barrier is related to a symmetry instability of the underlying Hartree–Fock mean-field solution, leading to orbitals representing two +0.5-fold charged ions in the limit of separated fragments. This, in turn, leads to a wrong 1/R asymptote of the interaction potential computed by perturbation-based CC approximations. Physically meaningful perturbative corrections in the long-range tail of the PEC may instead be obtained using symmetry-broken reference determinants.
%0 Journal Article
%1 Schnabel_Cheng_Köhn_2021
%A Schnabel, Jan
%A Cheng, Lan
%A Köhn, Andreas
%D 2021
%J The Journal of Chemical Physics
%K chemie koehn myown from:akoehn köhn theoretische stuttgart
%P 124101
%R 10.1063/5.0062098
%T Limitations of perturbative coupled-cluster approximations for highly accurate investigations of Rb₂⁺
%U https://dx.doi.org/10.1063/5.0062098
%V 155
@article{Schnabel_Cheng_Köhn_2021,
abstractnote = {We reveal limitations of several standard coupled-cluster (CC) methods with perturbation-theory based noniterative or approximate iterative treatments of triple excitations when applied to the determination of highly accurate potential energy curves (PECs) of ionic dimers, such as the XΣg+2 electronic ground state of Rb2+. Such computations are of current interest for the understanding of ion–atom interactions in the ultracold regime. We demonstrate that these CC methods lead to an unphysical long-range barrier for the Rb2+ system. The barrier is small but spoils the long-range behavior of the PEC. The effect is also found for other X2+ systems, such as X = Li, Na, and K. Calculations using a flexible framework for obtaining leading perturbative triples corrections derived using an analytic CC singles and doubles energy derivative formulation demonstrate that the origin of this problem lies in the use of T̂3 amplitudes obtained from approximate CC singles, doubles, and triples amplitude equations. It is shown that the unphysical barrier is related to a symmetry instability of the underlying Hartree–Fock mean-field solution, leading to orbitals representing two +0.5-fold charged ions in the limit of separated fragments. This, in turn, leads to a wrong 1/R asymptote of the interaction potential computed by perturbation-based CC approximations. Physically meaningful perturbative corrections in the long-range tail of the PEC may instead be obtained using symmetry-broken reference determinants.},
added-at = {2021-10-07T21:21:14.000+0200},
author = {Schnabel, Jan and Cheng, Lan and Köhn, Andreas},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/26c3790f3a69001759fd481656dcbe1c2/theochem},
doi = {10.1063/5.0062098},
interhash = {767d97da3699ff33ba206d9aa488694a},
intrahash = {6c3790f3a69001759fd481656dcbe1c2},
issn = {0021-9606},
journal = {The Journal of Chemical Physics},
keywords = {chemie koehn myown from:akoehn köhn theoretische stuttgart},
pages = 124101,
timestamp = {2021-10-07T19:21:14.000+0200},
title = {Limitations of perturbative coupled-cluster approximations for highly accurate investigations of Rb₂⁺},
url = {https://dx.doi.org/10.1063/5.0062098},
volume = 155,
year = 2021
}
