Separation of metric in Wick's theorem.

Abstract

In quantum chemistry, Wick's theorem is an important tool to reduce products of fermionic creation and annihilation operators. It is especially useful in computations employing reference states. The original theorem has been generalized to tackle multiconfigurational wave functions or nonorthogonal orbitals. One particular issue of the resulting structure is that the metric and density matrices are intertwined despite their different origin. Here, an alternative, rather general tensorial formulation of Wick's theorem is proposed. The main difference is the separation of the metric-the coefficients at normal-ordered operators become products of an n-electron density matrix element and the Pfaffian of a matrix formed by orbital overlaps. Different properties of the formalism are discussed, including the use of density cumulants, the particle-hole symmetry, and applications to transition density matrices, i.e., the case of different bra and ket reference states. The metric-separated version of Wick's theorem provides a platform for the derivation of various quantum chemical methods, especially those complicated by non-trivial reference states and nonorthogonality issues.