The Simplest Possible Approach for Simulating S0- S1 Conical Intersections with DFT/TDDFT: Adding One Doubly Excited Configuration.

Abstract

A simple combination of density functional theory/time-dependent density functional theory (DFT/TDDFT) and configuration interaction is presented to fix the incorrect topology of the S0- S1 conical intersection (CI) and allow a description of bond making and bond breaking in photoinduced dynamics. The proposed TDDFT-1D method includes one lone optimized doubly excited configuration in addition to the DFT/TDDFT singly excited states within the context of a large configuration interaction Hamiltonian. Results for ethylene and stilbene are provided to demonstrate that this ansatz can yield physically meaningful potential energy surfaces near S0- S1 avoided crossings without changing the vertical excitation energies far from the relevant crossings. We also investigate the famous linear water example to show that the algorithm calculates the correct topology of the S0- S1 CI and yields the correct geometric phase.