Reduced Density Matrix Cumulants: The Combinatorics of Size-Consistency and Generalized Normal Ordering Jonathon P. Misiewicz, Justin M. Turney, and Henry F. Schaefer III∗ Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia, 30602 E-mail:
[email protected] Abstract Reduced density matrix cumulants play key roles in the theory of both reduced den- sity matrices and multiconfigurational normal ordering, but the underlying formalism has remained mysterious. We present a new, simpler generating function for reduced density matrix cumulants that is formally identical to equating the coupled cluster and configuration interaction ans¨atze.This is shown to be a general mechanism to convert between a multiplicatively separable quantity and an additively separable quantity, as defined by a set of axioms. It is shown that both the cumulants of probability theory and reduced density matrices are entirely combinatorial constructions, where the differences can be associated to changes in the notion of \multiplicative separabil- ity" for expectation values of random variables compared to reduced density matrices. We compare our generating function to that of previous works and criticize previous claims of probabilistic significance of the reduced density matrix cumulants. Finally, we present the simplest proof to date of the Generalized Normal Ordering formalism to explore the role of reduced density matrix cumulants therein. 1 1 Introduction Reduced density matrix cumulants are fundamental in both reduced density matrix (RDM) theories and multireference theories that use the generalized normal ordering formalism (GNO) of Kutzelnigg and Mukherjee.1{5 To RDM theories, RDM cumulants are the size- consistent parts of the RDMs. This is one of the primary reasons why cumulants are either parameterized or varied directly in many RDM-based theories.6{11 In GNO, second quan- tized operators are decomposed into linear combinations of operators \normal ordered" with respect to an arbitrary reference, Ψ, via the Generalized Wick's Theorem.