A full variational calculation based on a tensor product decomposition

Abstract

A new direct full variational approach exploits a tensor (Kronecker) product decomposition of the Hamiltonian. Explicit assembly and storage of the Hamiltonian matrix is avoided by using the Kronecker product structure to form matrix-vector products directly from the molecular integrals. Computation-intensive integral transformations and formula tapes are unnecessary. The wavefunction is expanded in terms of spin-free primitive kets rather than Slater determinants or configuration state functions, and the expansion is equivalent to a full configuration interaction expansion. The approach suggests compact storage schemes and algorithms which are naturally suited to parallel and pipelined machines.