Fundamental Variable and Density Representation in Multistate DFT for Excited States.

Abstract

Complementary to the theorems of Hohenberg and Kohn for the ground state, Theophilou's subspace theory establishes a one-to-one relationship between the total eigenstate energy and density ρV(r) of the subspace spanned by the lowest N eigenstates. However, the individual eigenstate energies are not directly available from such a subspace density functional theory. Lu and Gao (J. Phys. Chem. Lett. 2022, 13, 7762) recently proved that the Hamiltonian projected on to this subspace is a matrix functional of the multistate matrix density D(r) and that variational optimization of the trace of the Hamiltonian matrix functional yields exactly the individual eigenstates and densities. This study shows that the matrix density D(r) is the necessary fundamental variable in order to determine the exact energies and densities of the individual eigenstates. Furthermore, two ways of representing the matrix density are introduced, making use of nonorthogonal and orthogonal orbitals. In both representations, a multistate active space of auxiliary states can be constructed to exactly represent D(r) with which an explicit formulation of the Hamiltonian matrix functional is presented. Importantly, the use of a common set of orthonormal orbitals makes it possible to carry out multistate self-consistent-field optimization of the auxiliary states with singly and doubly excited configurations (MS-SDSCF).