REDUCED MULTIREFERENCE COUPLED-CLUSTER METHOD AND ITS APPLICATION TO THE PYRIDYNE DIRADICALS

Abstract

The reduced multireference (RMR) coupled-cluster (CC) method with singles and doubles (RMR CCSD) that employs a modest-size MR CISD wave function as an external source for the most important (primary) triples and quadruples in order to account for the nondynamic correlation effects in the presence of quasidegeneracy, and which is further perturbatively corrected for the remaining (secondary) triples, RMR CCSD(T), is employed to compute the molecular geometry and the energy of the lowest-lying singlet and triplet states, as well as the corresponding singlet–triplet splitting, for all possible isomers of the m, n-pyridyne diradicals. A comparison is made with earlier results that were obtained by other authors, and the role of the multireference effects for both the geometry and the spin multiplicity of the lowest state, as described by the RMR-type methods, is demonstrated on the example of 2,6- and 3,5-pyridynes.