A coupled cluster treatment of intramonomer electron correlation within symmetry-adapted perturbation theory: benchmark calculations and a comparison with a density-functional theory description

作者：Korona Tatiana^*

来源：Molecular Physics, 2013, 111(24): 3705-3715.

DOI：10.1080/00268976.2012.746478

• intermolecular interaction
• symmetry-adapted perturbation theory
• coupled cluster theory
• SAPT(CCSD)
• SAPT(DFT)

Symmetry-adapted perturbation theory (SAPT) with intramonomer electron correlation described by coupled cluster theory limited to single and double excitations was applied to 21 noncovalent complexes in their minimum geometries. The resulting benchmark contributions to the interaction energy were utilized to examine the accuracy of a more approximate variant of the SAPT method, where interacting molecules are described by density functional theory (DFT) with different functionals, like LDA, PBE, B3LYP, PBE0, M05, M05-2X, M06, and M06-2X (in all cases the asymptotic correction for the exchange-correlation functional has been utilized). Average errors for individual energy components of SAPT(DFT) are not larger than 10% for best functionals under study. Among the tested functionals PBE0, M05, and B3LYP should be especially recommended for the SAPT(DFT) approach. The M06 functional gives the largest errors with respect to SAPT(CCSD) and should not be used for describing intramonomer correlation in SAPT.

• 出版日期2013-12-1