Multistate Density Functional Theory of Excited States

We report a rigorous formulation of density functional theory for excited states, providing a theoretical foundation for a multistate density functional theory. We prove the existence of a Hamiltonian matrix functional [D] of the multistate matrix density D(r) in the subspace spanned by the lowest N eigenstates. Here, D(r) is an N-dimensional matrix of state densities and transition densities. Then, a variational principle of the multistate subspace energy is established, whose minimization yields both the energies and densities of the individual N eigenstates. Furthermore, we prove that the N- dimensional matrix density D(r) can be sufficiently represented by N-2 nonorthogonal Slater determinants, based on which an interacting active space is introduced for practical calculations. This work establishes that the ground and excited states can be treated on an equal footing in density functional theory.

Automated summary

This paper presents a rigorous formulation of density functional theory for excited states, providing a theoretical foundation for multistate density functional theory. The existence of a Hamiltonian matrix functional for the multistate matrix density is proven, and a variational principle for the multistate subspace energy is established. It is also shown that the N-dimensional matrix density can be represented by N-2 nonorthogonal Slater determinants.