Correlation Problems in Atomic and Molecular Systems. IV. Extended Coupled-Pair Many-Electron Theory and Its Application to the BH3Molecule

The equations of the coupled-pair many-electron theory (CPMET) are extended to incorporate the effect of both unlinked and linked triexcited clusters. The minimal basis correlation energy of the B${\mathrm{H}}_3$ molecule in the ground state is calculated using the ordinary as well as extended CPMET in various degrees of approximation, and the relative importance of linked and unlinked triexcited clusters is studied. The results afford an unambiguous conclusion for closed-shell systems that, in contrast to the situation with tetraexcited states, unlinked triexcited clusters are negligible relative to the linked ones. It is shown that the extended CPMET reproduces the full configuration-interaction results to a very high degree of accuracy.