Integrated experimental and computational spectroscopy study on π-stacking interaction: the anisole dimer
Literature Information
Nicola Schiccheri, Massimiliano Pasquini, Giovanni Piani, Giangaetano Pietraperzia, Maurizio Becucci, Vincenzo Barone
Integrated experimental and computational results help to clarify the nature of the intermolecular interactions in a simple, isolated π-stacked dimer prepared in a molecular beam. The properties of bimolecular anisole complexes are examined and discussed in terms of the local/supramolecular nature of the electronic wavefunctions. Experimental resonance-enhanced multi-photon ionization spectra of clusters with different isotopic compositions confirmed the fundamentally localized nature of the S1 ← S0 electronic transition. A detail analysis of the experimental results however shows the existence of non-negligible excitonic coupling for the excited-state wavefunctions leading to the doubling of the single-molecule vibronic levels in the S1 state, with a splitting of about 30 cm−1. Theoretical simulation of the vibrationally resolved electronic spectra and computations of the excitonic coupling convincingly support the experimental findings. The overall combined experimental/theoretical study allows a detailed description of the stacking interaction in the anisole dimer.
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