Dimer formation of perylene: an ultracold spectroscopic and computational study

Abstract

The electronic spectra of perylene inside helium nanodroplets recorded by the depletion method are presented. The results show two broad peaks in addition to sharp monomer vibronic transitions due to dimer formation. In order to understand the details of the spectra, first the dimer formation is studied by DFT and SCS-MP2 calculations and then the electronic spectra are calculated at the minima of the potential energy surface (PES). Theoretical calculations show that there are two low-lying energetically degenerate dimer structures; namely a parallel displaced one and a rotated stacked one. PES around these minima is very flat with a number of local minima at higher energies which at the experimental temperatures cannot be populated. Even though thermodynamically these two structures are equally populated, dynamical considerations point out that in helium droplet the parallel displaced geometry is encouraged by the natural alignment of the molecules due to the acquired angular momentum following the pick-up process. The calculated spectrum of the parallel displaced geometry predicts the positions of the dimer transitions within 30 nm of the experimental spectrum. Furthermore, the difference between the two dimer transitions is accurately predicted to be about 25 nm while the experimental difference was about 20 nm. Such a small difference could only be detected due to the ultracold conditions helium nanodroplets provided.