Computational determination of accurate bond energies of dispersion-dominated systems in the gas phase

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The primary aim of the project is the accurate determination of ground- and excited-state dissociation energies (D0) and electronic binding energies (De) of dispersion-dominated complexes of (hetero-)aromatic molecules (denoted M) with dispersively bound solvents (denoted S) using computational methods. Examples are complexes of M = carbazole, 1-naphthol with S = Ne−Xe, N2, CO. Accurate experimental data are available from stimulated-emission pumping/resonant two-photon ionization (SEP/R2PI) spectroscopy. Computationally, a combination of (dispersion-corrected) density-functional theory and high-level coupled-cluster methods will be applied, which include explicitly-correlated wave functions in order to converge quickly to the limit of a complete basis-set expansion. The established De and D0 values will serve as benchmarks for the development of novel computational methods including explicitly-correlated symmetry-adapted perturbation theory and Green's function-based methods. It is expected that the combined experimental/theoretical benchmarks as well as the new computational methods will be useful for other projects of the Priority Programme.