Physical and mathematical content of coupled–cluster equations: Correspondence between coupled–cluster and configuration–interaction solutions

Abstract

To gain more insight into the physical and mathematical content of the equations of the coupled–cluster (CC) method, comprehensive numerical studies have been performed for various geometries of the H4 model which belongs to the simplest and best understood among the realistic many–electron model systems. These studies are for the first time based on the knowledge of the complete sets of geometrically isolated solutions of the relevant equations that are obtained when using a special version of the homotopy methods. The equations of the CC method including two–electron excitations (CCD) both in the spin–orbital and spin–symmetry–adapted versions are considered. To establish the correspondence of the solutions attained with those of the configuration interaction (CID) method, we have for the first time solved the unabridged characteristic equations (CE) of T. P. Živković and H. J. Monkhorst [J. Math. Phys. 19, 1007 (1978)]. The complete sets of solutions to the spin–orbital and spin–symmetry–adapted versions of the CCD equations and CEs consist of 20 and 12 solutions, respectively. Their structures turned out to be unexpectedly simple, which makes it possible to understand the physical and mathematical significance of the individual solutions. Moreover, this simplicity rises hopes that the most serious irregularities previously found for low dimensional simulations of the CEs can be avoided for realistic systems. The present results confirm most of the findings of previous research. Attention is paid to studies of the impact of using mixed–symmetry cluster operators on the structure of solutions to the CC equations. The specific part played by the components of the cluster amplitudes corresponding to other spin–symmetry than that of the reference function has been demonstrated for the first time.