Electronic Spectroscopy in Superfluid Helium Droplets

Abstract

AbstractElectronic 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.