State-specific multireference complete-active-space coupled-cluster approach versus other quantum chemical methods: dissociation of the N₂ molecule

Abstract

A comprehensive comparison of different quantum-chemical methods applied to calculate the N₂ ground state potential energy curve is presented. In the comparison we highlight the multireference state-specific (MRSS) coupled-cluster (CC) approach with the complete-active-space (CAS) reference and with single and double excitations from all reference determinants in the CC operator developed in our group. The method is called CASCCSD. The energy and amplitude equations for the method and the corresponding computer code have been generated using a computerized automative procedure that in the present work was extended to produce a parallel computer code. The complete CASCCSD wave function for N₂ includes some selected eight-fold excitations in the CC operator. An analysis of the wave function estimates the importance of those excitations at large internuclear separations.

Acknowledgements

This work has been supported by the National Science Foundation. DIL would like to thank the Kharkiv National University Foundation for partial support of his contribution to this work.