A Constraint-Based Orbital-Optimized Excited State Method (COOX)

Abstract

In this work, we present a novel method to directly calculate targeted electronic excited states within a self-consistent field calculation based on constrained density functional theory (cDFT). The constraint is constructed from the static occupied-occupied and virtual-virtual parts of the excited state difference density from (simplified) linear-response time-dependent density functional theory calculations (LR-TDDFT). Our new method shows a stable convergence behavior, provides an accurate excited state density adhering to the Aufbau principle, and can be solved within a restricted SCF for singlet excitations to avoid spin contamination. This also allows the straightforward application of post-SCF electron-correlation methods like MP2 or direct RPA methods. We present the details of our constraint-based orbital-optimized excited state method (COOX) and compare it to similar schemes. The accuracy of excitation energies will be analyzed for a benchmark of systems, while the quality of the resulting excited state densities is investigated by evaluating excited state nuclear forces and excited state structure optimizations. We also investigate the performance of the proposed COOX method for long-range charge transfer excitations and conical intersections with the ground-state.