Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations.

Abstract

We recently proposed domain separated density functional theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. This work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: (i), the screened-density approximation (SDA) and (ii) linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.