Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn-Sham orbitals be more beneficial than Hartree-Fock orbitals?

Benedek, Zsolt and Tímár, Paula and Szilvasi, T. and Barcza, Gergely (2022) Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn-Sham orbitals be more beneficial than Hartree-Fock orbitals? JOURNAL OF COMPUTATIONAL CHEMISTRY, 43 (32). pp. 2103-2120. ISSN 0192-8651

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Abstract

Coupled cluster calculations are traditionally performed over Hartree–Fock reference orbitals (HF-CC methodology). However, in the literature it has been repeatedly raised whether the use of a Kohn–Sham reference (KS-CC methodology) might result in improved performance relative to HF-CC. In the present study, we re-examine the relation of HF-CC and KS-CC methods by comparing the results of widely applied truncated CC calculations (CCSD, CCSD(T), CCSDT) to the limit of full configuration interaction (FCI), which serves as an undebatable reference point of accuracy. Based on a series of CC calculations on diatoms and transition metal complexes, we demonstrate that no systematic improvement of coupled cluster electronic energies, densities and chemical reaction energies is expected when changing from HF to a KS reference. Nevertheless, fortuitous error cancellations might occasionally result in illusory improvement compared to HF-CC. Altogether, the application of KS-CC is not advantageous over HF-CC, but it is also not unreasonable as the choice of reference has negligible influence on the results at sufficiently high CC levels. In addition, KS-CC can be a particularly useful alternative if difficulties are encountered in HF or HF-CC convergence. It is also notable that KS-CC results are found to be practically independent of the chosen density functional, which implies that almost any KS-CC method can be used in place of HF-CC.

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