Superfluid helium nanodroplets comprised of thousands to millions of helium atoms can serve as a reactor for the synthesis of heterogeneous molecular clusters at cryogenic conditions. The cluster synthesis occurs via consecutive pick-up of the cluster building blocks by the helium droplet and their subsequent coalescence within the droplet. The effective collision cross section of the building blocks is determined by the helium droplet size and thus exceeds by orders of magnitude that of a reactive collision in the gas phase. Moreover, the cryogenic helium environment (at 0.38 K) as a host promotes the formation of metastable cluster configurations. The question arises as to the extent of the actual involvement of the helium environment in the cluster formation. The present study deals with clusters of single phthalocyanine (Pc) molecules with single water molecules. A large fluorophore such as Pc offers several sites where the water molecule can attach. The resulting isomeric variants of the Pc−H 2 O complex can be selectively identified by electronic spectroscopy. We compare the experimental electronic spectra of the Pc− H 2 O complex generated in superfluid helium nanodroplets with the results of quantum-chemical calculations on the same cluster but under gas-phase conditions. The number of isomeric variants observed in the helium droplet experiment comes out the same as that obtained from our gas-phase calculations.

Spectroscopic investigation of phthalocyanine in the gas phase has tremendously profitted from molecular beam spectroscopy. Isentropic expansion accomplishes to reduce the population of rovibrational states to the vibrational ground state...

Electronic spectroscopy has been instrumental in demonstrating the properties of helium droplets as a cryogenic matrix for molecules. The electronic spectrum of glyoxal, which was one of the first molecules investigated in helium droplets by means of electronic spectroscopy, showed two features that provided convincing evidence that the droplets were superfluid. These were free rotation and the distinct shape of the phonon side band which could be directly assigned to the characteristic dispersion curve of a superfluid. On closer examination, however, details such as increased moments of inertia and a spectral response on the droplet size distribution revealed unexpected features of microsolvation in the superfluid helium. In the course of studying many different molecules, it has become clear that electronic spectroscopy in helium droplets provides insight into the detailed effects of microsolvation. These in turn lead to numerous questions regarding the interaction with the superfluid which are discussed in this chapter. In addition, the influence of microsolvation in helium droplets on van der Waals clusters generated inside helium droplets are discussed. Finally, the effect of helium solvation on unimolecular or bimolecular elementary chemical reactions is evaluated in comparison with corresponding experiments in the gas phase. Particular focus of this article lies on the spectral features related to helium solvation which are not yet fully understood.