Absolutely Localized Projection-Based Embedding for Excited States

Abstract

We present a quantum embedding method that allows for calculation of local excited states embedded in a Kohn–Sham density functional theory (DFT) environment. Projection-based quantum embedding methodologies provide a rigorous framework for performing DFT-in-DFT and wave function in DFT (WF-in-DFT) calculations. The use of absolute localization, where the density of each subsystem is expanded in only the basis functions associated with the atoms of that subsystem, provide improved computationally efficiency for WF-in-DFT calculations by reducing the number of orbitals in the WF calculation. In this work, we extend absolutely localized projection-based quantum embedding to study localized excited states using EOM-CCSD-in-DFT and TDDFT-in-DFT. The embedding results are highly accurate compared to the corresponding canonical EOM-CCSD and TDDFT results on the full system, with TDDFT-in-DFT frequently more accurate than canonical TDDFT. The absolute localization method is shown to eliminate the spurious low-lying excitation energies for charge-transfer states and prevent overdelocalization of excited states. Additionally, we attempt to recover the environment response caused by the electronic excitations in the high-level subsystem using different schemes and compare their accuracy. Finally, we apply this method to the calculation of the excited-state energy of green fluorescent protein and show that we systematically converge to the full system results. Here we demonstrate how this method can be useful in understanding excited states, specifically which chemical moieties polarize to the excitation. Furthermore, this work shows absolutely localized projection-based quantum embedding can treat local electronic excitations accurately and make computationally expensive WF methods applicable to systems beyond current computational limits.