The resolution of identity and chain of spheres approximations for the LPNO-CCSD singles Fock term

Abstract

In the present work, the RIJCOSX approximation, developed earlier for accelerating the SCF procedure, is applied to one of the limiting factors of LPNO-CCSD calculations: the evaluation of the singles Fock term. It turns out that the introduction of RIJCOSX in the evaluation of the closed shell LPNO-CCSD singles Fock term causes errors below the microhartree limit. If the proposed procedure is also combined with RIJCOSX in SCF, then a somewhat larger error occurs, but reaction energy errors will still remain negligible. The speedup for the singles Fock term only is about 9–10 fold for the largest basis set applied. For the case of Penicillin using the def2-QZVPP basis set, a single point energy evaluation takes 2 day 16 h on a single processor leading to a total speedup of 2.6 as compared to a fully analytic calculation. Using eight processors, the same calculation takes only 14 h.

Keywords:

• LPNO-CCSD
• RIJCOSX
• local methods
• coupled cluster theory