Efficient Adiabatic Connection Approach for Strongly Correlated Systems: Application to Singlet-Triplet Gaps of Biradicals.

ABSTRACT: Strong electron correlation can be captured with multireference wave function methods, but an accurate description of the electronic structure requires accounting for the dynamic correlation, which they miss. In this work, a new approach for the correlation energy based on the adiabatic connection (AC) is proposed. The AC_n method accounts for terms up to order n in the coupling constant, and it is size-consistent and free from instabilities. It employs the multireference random phase approximation and the Cholesky decomposition technique, leading to a computational cost growing with the fifth power of the system size. Because of the dependence on only one- and two-electron reduced density matrices, AC_n is more efficient than existing ab initio multireference dynamic correlation methods. AC_n affords excellent results for singlet-triplet gaps of challenging organic biradicals. The development presented in this work opens new perspectives for accurate calculations of systems with dozens of strongly correlated electrons.

SUBMITTER: Drwal D 

PROVIDER: S-EPMC9150121 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature