Abstract
The empirical model explaining microsolvation of molecules in superfluid helium droplets proposes a non-superfluid helium solvation layer enclosing the dopant molecule. This model warrants an empirical explanation of any helium induced substructure resolved for electronic transitions of molecules in helium droplets. Despite a wealth of such experimental data, quantitative modeling of spectra is still in its infancy. The theoretical treatment of such many-particle systems dissolved into a quantum fluid is a challenge. Moreover, the success of theoretical activities relies also on the accuracy and self-critical communication of experimental data. This will be elucidated by a critical resume of our own experimental work done within the last ten years. We come to the conclusion that spectroscopic data and among others in particular the spectral resolution depend strongly on experimental conditions. Moreover, despite the fact that none of the helium induced fine structure speaks against the empirical model for solvation in helium droplets, in many cases an unequivocal assignment of the spectroscopic details is not possible. This ambiguity needs to be considered and a careful and critical communication of experimental results is essential in order to promote success in quantitatively understanding microsolvation in superfluid helium nanodroplets.
Highlights
One of the first helium induced fine structures reported for electronic spectroscopy in superfluid helium droplets was a doublet splitting of all zero phonon lines (ZPL) accompanied by a phonon wing (PW) with an unexpected spectral shape for tetracene (Tc) as dopant species (Hartmann et al, 1998)
EXPERIMENTAL RESULTS The signature of microsolvation is omnipresent in spectroscopy of molecules in helium droplets
Our own experimental work on electronic spectroscopy of molecules or molecular aggregates inside superfluid helium nanodroplets will be reinvestigated with the focus on helium induced spectral features and their consistent interpretation
Summary
One of the first helium induced fine structures reported for electronic spectroscopy in superfluid helium droplets was a doublet splitting of all zero phonon lines (ZPL) accompanied by a phonon wing (PW) with an unexpected spectral shape for tetracene (Tc) as dopant species (Hartmann et al, 1998). As the model of a non-superfluid helium solvation layer justifies all the helium induced fine structures recorded so far in electronic spectra, the fine structures provide evidence for the helium solvation layer. While this empirical model proposed about two decades ago is generally accepted, a quantitative simulation of the helium induced fine structures has not be seen so far. The discussion on the helium induced fine structure of Tc is the motivation for a critical presentation of our own experimental work www.frontiersin.org
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