Definition and benchmarking of ab initio fragment methods for accurate excimer potential energy surfaces

Abstract

While Coupled-Cluster methods have been proven to provide an accurate description of excited electronic states, the scaling of the computational costs with the system size limits the degree for which these methods can be applied. In this study a fragment-based approach is presented for non-covalently bound molecular complexes with interacting chromophores of the fragments (so called Frenkel pairs), such as pi-stacked nucleobases. The interaction of the fragments is considered at two distinct steps. First, the states localized on the fragments are described in the presence of the other fragment(s); for this we test two approaches. One method is founded on QM/MM principles, only including the electrostatic interaction between the fragments in the electronic structure calculation with Pauli repulsion and dispersion effects added separately. The other model, a Projection-based Embedding (PbE) using the Huzinaga equation includes both electrostatic and Pauli repulsion and only needs to be augmented by dispersion interactions. In both schemes the extended Effective Fragment Potential (EFP2) method of Gordon et al. was found to provide an adequate correction for the missing terms. In the second step, the interaction of the localized chromophores is modeled for a proper description of the excitonic coupling. Here the inclusion of purely electrostatic contributions appears to be sufficient: it is found that the Coulomb part of the coupling, as evaluated by the transition density cube method, provides accurate splitting of the energies of interacting chromophores that are separated by more than 4 Angstrom.