Foundation of One-Particle Reduced Density Matrix Functional Theory for Excited States.

In Phys. Rev. Lett. 2021, 127, 023001 a reduced density matrix functional theory (RDMFT) was proposed for calculating energies of selected eigenstates of interacting many-Fermion systems. Here, we develop a solid foundation for this so-called w-RDMFT and present the details of various derivations. First, we explain how a generalization of the Ritz variational principle to ensemble states with fixed weights w in combination with the constrained search would lead to a universal functional of the one-particle reduced density matrix. To turn this into a viable functional theory, however, we also need to implement an exact convex relaxation. This general procedure includes Valone's pioneering work on ground state RDMFT as the special case w = (1,0, ···). Then, we work out in a comprehensive manner a methodology for deriving a compact description of the functional's domain. This leads to a hierarchy of generalized exclusion principle constraints which we illustrate in great detail. By anticipating their future pivotal role in functional theories and to keep our work self-contained, several required concepts from convex analysis are introduced and discussed.

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