Linearized Pair-Density Functional Theory

Multiconfiguration pair-density functional theory (MC-PDFT) is a post-SCF multireference method that has been successful at computing ground- and excited-state energies. However, MC-PDFT is a single-state method in which the final MC-PDFT energies do not come from diagonalization of a model-space Hamiltonian matrix, and this can lead to inaccurate topologies of potential energy surfaces near locally avoided crossings and conical intersections. Therefore, in order to perform physically correct <i>ab initio</i> molecular dynamics with electronically excited states or to treat Jahn-Teller instabilities, it is necessary to develop a PDFT method that recovers the correct topology throughout the entire nuclear configuration space. Here we construct an effective Hamiltonian operator, called the linearized PDFT (L-PDFT) Hamiltonian, by expanding the MC-PDFT energy expression to first order in a Taylor series of the wave function density. Diagonalization of the L-PDFT Hamiltonian gives the correct potential energy surface topology near conical intersections and locally avoided crossings for a variety of challenging cases including phenol, methylamine, and the spiro cation. Furthermore, L-PDFT outperforms MC-PDFT and previous multistate PDFT methods for predicting vertical excitations from a variety of representative organic chromophores.