Journal of Chemical Physics, Vol.111, No.18, 8356-8365, 1999
Possibilities for a density matrix theory
Two possible routes are considered to arrive at a one-particle reduced density matrix formulation of electronic structure theory. In the first scheme, an extended Fock matrix H is defined that has twice the dimension of the one-particle basis set. The corresponding Green's function, defined as the upper left block of (omega 1-H)(-1), yields the exact one-particle density matrix and energy. The poles of the Green's function are precisely the ionization potentials and electron affinities of the extended Koopmans theorem. In the second scheme, a generalized Fock equation [F(rho),rho] = X is derived that is satisfied by the exact non-idempotent one-particle density matrix. The antisymmetric matrix X on the right-hand side is obtained from the irreducible part of the two-particle reduced density matrix, while F is the usual Fock matrix defined using the correlated one-matrix. The generalized Fock equation is a necessary condition but does not determine r uniquely. Alternatively, the one-matrix can be obtained from the irreducible part of the two-matrix directly, using a sum rule. The analysis leads to some additional desiderata and separability properties that may be imposed on traditional wave function based approaches. Possibilities for practical computational schemes are addressed briefly.