Can density cumulant functional theory describe static correlation effects?

نویسندگان

  • J Wayne Mullinax
  • Alexander Yu Sokolov
  • Henry F Schaefer
چکیده

We evaluate the performance of density cumulant functional theory (DCT) for capturing static correlation effects. In particular, we examine systems with significant multideterminant character of the electronic wave function, such as the beryllium dimer, diatomic carbon, m-benzyne, 2,6-pyridyne, twisted ethylene, as well as the barrier for double-bond migration in cyclobutadiene. We compute molecular properties of these systems using the ODC-12 and DC-12 variants of DCT and compare these results to multireference configuration interaction and multireference coupled-cluster theories, as well as single-reference coupled-cluster theory with single, double (CCSD), and perturbative triple excitations [CCSD(T)]. For all systems the DCT methods show intermediate performance between that of CCSD and CCSD(T), with significant improvement over the former method. In particular, for the beryllium dimer, m-benzyne, and 2,6-pyridyne, the ODC-12 method along with CCSD(T) correctly predict the global minimum structures, while CCSD predictions fail qualitatively, underestimating the multireference effects. Our results suggest that the DC-12 and ODC-12 methods are capable of describing emerging static correlation effects but should be used cautiously when highly accurate results are required. Conveniently, the appearance of multireference effects in DCT can be diagnosed by analyzing the DCT natural orbital occupations, which are readily available at the end of the energy computation.

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عنوان ژورنال:
  • Journal of chemical theory and computation

دوره 11 6  شماره 

صفحات  -

تاریخ انتشار 2015