Exploiting regularity in systematic sequences of wavefunctions which approach the full CI limit

Summary The ground state total energy and related 1-electron properties are computed for three small molecules (N₂, H₂O, and H₂CN) using several systematic sequences of wavefunctions which approach the full CI. These sequences include multireference CI, averaged coupled pair functional and quasidegenerate variational perturbation theory wavefunctions. It is demonstrated that sufficient regularity exists in the sequence of variationally computed energies to permit extrapolation to the full CI limit using simple analytic expressions. It is furthermore demonstrated that a subset of the original list of configurations employed in the normal singles and doubles CI procedure can be selected using second order perturbation theory without adversely affecting the extrapolation to the full CI limit. This significantly broadens the range of applicability of the method. Along these lines, a scheme is proposed for the extrapolation of the selected CI results to the zero threshold (i.e. unselected) values in cases where the numbers of configurations associated with the latter would render the calculations intractable. Due to the vast reduction in the number of configurations which are handled variationally, the proposed scheme makes it possible to derive estimates of the full CI limit in cases where explicit full CI is either very difficult or currently impossible.Dedicated to Prof. Klaus RuedenbergThe Pacific Northwest Laboratory is operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC06-76RLO 1830