Benchmarking Aspects of Ab Initio Fragment Models for Accurate Excimer Potential Energy Surfaces

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 work different aspects of fragment-based approaches are studied on noncovalently bound molecular complexes with interacting chromophores of the fragments, 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 provides accurate splitting of the energies of interacting chromophores that are separated by more than 4 & ANGS;.

Automated summary

Although Coupled-Cluster methods accurately describe excited electronic states, their computational costs limit their application. This study focuses on fragment-based approaches for noncovalently bound molecular complexes with interacting chromophores. Two approaches were tested for describing the states localized on the fragments with electrostatic interactions, Pauli repulsion, and dispersion effects. The effective fragment potential method was found to provide an adequate correction. Electrostatic contributions were sufficient for modeling the interaction of the localized chromophores.