Convergence of the Interaction Energies in Noncovalent Complexes in the Coupled-Cluster Methods Up to Full Configuration Interaction Lucia Šimová Jan Řezáč Pavel Hobza 10.1021/ct4002762.s001 https://acs.figshare.com/articles/journal_contribution/Convergence_of_the_Interaction_Energies_in_Noncovalent_Complexes_in_the_Coupled_Cluster_Methods_Up_to_Full_Configuration_Interaction/2387974 The CCSD­(T) method stands out among various coupled-cluster (CC) approximations as the “golden standard” in computational chemistry and is widely and successfully used in the realm of covalent and noncovalent interactions. The CCSD­(T) method provides reliable interaction energies, but their surprising accuracy is believed to arise partially from an error compensation. The convergence of the CC expansion has been investigated up to fully iterative pentuple excitations (CCSDTQP); for the smallest eight electron complexes, the full CI calculations have also been performed. We conclude that the convergence of interaction energy at noncovalent accuracy (0.01 kcal/mol) for the complexes studied is reached already at CCSDTQ or CCSDT­(Q) levels. When even higher accuracy (spectroscopic accuracy of 1 cm<sup>–1</sup>, or 3 cal/mol) is required, then the noniterative CCSDTQ­(P) method could be used. 2013-08-13 00:00:00 CI calculations iterative pentuple excitations noncovalent interactions CCSD error compensation interaction energy spectroscopic accuracy method Noncovalent Complexes interaction energies Interaction Energies convergence electron complexes CCSDTQ CCSDTQP CC expansion CCSDT