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Towards a multiconfigurational method of increments

E. Fertitta and D. Koch and B. Paulus and G. Barcza and Ö. Legeza – 2018

The method of increments (MoI) allows one to successfully calculate cohesive energies of bulk materials with high accuracy, but it encounters difficulties when calculating dissociation curves. The reason is that its standard formalism is based on a single Hartree-Fock (HF) configuration whose orbitals are localised and used for the many-body expansion. In situations where HF does not allow a size-consistent description of the dissociation, the MoI cannot be guaranteed to yield proper results either. Herein, we address the problem by employing a size-consistent multiconfigurational reference for the MoI formalism. This leads to a matrix equation where a coupling derived by the reference itself is employed. In principle, such an approach allows one to evaluate approximate values for the ground as well as excited states energies. While the latter are accurate close to the avoided crossing only, the ground state results are very promising for the whole dissociation curve, as shown by the comparison with density matrix renormalisation group benchmarks. We tested this two-state constant-coupling MoI on beryllium rings of different sizes and studied the error introduced by the constant coupling.

Towards a multiconfigurational method of increments
E. Fertitta and D. Koch and B. Paulus and G. Barcza and Ö. Legeza
DOI: 10.1080/00268976.2018.1444208
Molecular Physics 2018, 116:11, 1471-1482