Approximate Functionals for Multistate Density Functional Theory.

Abstract

Recently Lu and Gao [J. Phys. Chem. Lett. 2022, 13 (33), 7762-7769] published a new, rigorous density functional theory for excited states and proved that the projection of the kinetic and electron-repulsion operators into the subspace of the lowest electronic states are a universal functional of the matrix density D(r). This is the first attempt to find an approximation to the multistate universal functional . It is shown that (i) does not explicitly depend on the number of electronic states and (ii) is an analytic matrix functional. The Thomas-Fermi-Dirac-von Weizsäcker model and the correlation energy of the homogeneous electron gas are turned into matrix functionals guided by two principles: that each matrix functional should transform properly under basis set transformations and that the ground state functional should be recovered for a single electronic state. Lieb-Oxford-like bounds on the average kinetic and electron-repulsion energies in the subspace are given. When evaluated on the numerically exact matrix density of LiF, this simple approximation reproduces the matrix elements of the electron-repulsion operator in the basis of the exact eigenstates accurately for all bond lengths. In particular the off-diagonal elements of the effective Hamiltonian that come from the interactions of different electronic states can be calculated with the same or better accuracy than the diagonal elements. Unsurprisingly, the largest error comes from the kinetic energy functional. More exact conditions that constrain the functional form of are needed to go beyond the local density approximation.