Cumulant expansion of the reduced density matrices

摘要

k-particle cumulants #lambda#_k (for 2 <= k <= n) corresponding to the k-particle reduced density matrices #gamma#_k for an n-fermion system are defined via a generating function. The two-particle cumulant #lambda#_2 describes two-particle correlations (excluding exchange), #lambda#_3 genuine three-particle correlations etc. The properties of these cumulants are analyzed. Conditions for vanishing of certain #lambda#_k are formulated. Necessary and sufficient for #lambda#_2 = 0 is the well-known idempotency condition #gamma#~2 = #gamma# for #gamma# ident to #gamma#_1. For #lambda#_3 = 0 to hold, a general necessary conditions is Tr{2#gamma#~3 - 3#gamma#~2 + #gamma#} = 0, for three special forms of the wave function (arbitrary two-electron state, antisymmetrized product of strongly orthogonal geminals on antisymmetrized geminal lower wave function of extreme type) 2#gamma#~3 - 3#gamma#~2 + #gamma# = 0 turns out to be necessary and sufficient. For a multiconfiguration self-consistent field wave function the only nonvanishing matrix elements of the cumulants are those where all labels refer to active (partially occupied) spin orbitals. Spin-free cumulants #LAMBDA#_k corresponding to the spin-free reduced density matrices #GAMMA#_k are also defined and analyzed. The main interest in the density cumulants is in connection with the recently formulated normal ordering and the corresponding Wick theorem for arbitrary reference functions, but they are also useful for an analysis of electron correlation.