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Convergence of the Interaction Energies in Noncovalent Complexes in the Coupled-Cluster Methods Up to Full Configuration Interaction

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journal contribution
posted on 13.08.2013, 00:00 authored by Lucia Šimová, Jan Řezáč, Pavel Hobza
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–1, or 3 cal/mol) is required, then the noniterative CCSDTQ­(P) method could be used.