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A New Benchmark Set for Excitation Energy of Charge Transfer States: Systematic Investigation of Coupled-Cluster Type Methods

preprint
submitted on 14.02.2020 and posted on 18.02.2020 by Balázs Kozma, Attila Tajti, Baptiste Demoulin, Róbert Izsák, Marcel Nooijen, Péter Szalay
There are numerous publications on benchmarking quantum chemistry methods for excited states. These studies rarely include Charge Transfer (CT) states although many interesting phenomena in e.g. biochemistry and material physics involve transfer of electron between fragments of the system. Therefore, it is timely to test the accuracy of quantum chemical methods for CT states, as well. In this study we first suggest a set benchmark systems consisting of dimers having low-energy CT states. On this set, the excitation energy has been calculated with coupled cluster methods including triple excitations (CC3, CCSDT-3, CCSD(T)(a)* ), as well as with methods including full or approximate doubles (CCSD, STEOM-CCSD, CC2, ADC(2), EOM-CCSD(2)). The results show that the popular CC2 and ADC(2) methods are much more inaccurate for CT states than for valence states. On the other hand, CCSD seems to have similar systematic overestimation of the excitation energies for both valence and CT states. Concerning triples methods, the new CCSD(T)(a)* method including non-iterative triple excitations preforms very well for all type of states, delivering essentially CCSDT quality results.

Funding

NKFI 124293

NKIF 124018

History

Email Address of Submitting Author

szalay@chem.elte.hu

Institution

ELTE Eötvös Loránd University

Country

Hungary

ORCID For Submitting Author

0000-0003-1885-3557

Declaration of Conflict of Interest

None

Version Notes

version 1.0

Exports