TY - JOUR A1 - Pentlehner, Dominik A1 - Riechers, R. A1 - Vdovin, A. A1 - Pötzl, G.M. A1 - Slenczka, A. T1 - Electronic spectroscopy of molecules in superfluid helium nanodroplets: an excellent sensor for intramolecular charge redistribution JF - The Journal of Physical Chemistry, Special Issue: J. Peter Toennies Festschrift N2 - Electronic spectra of molecules doped into superfluid 4He nanodroplets reveal important details of the microsolvation in superfluid helium. The vibrational fine structure in the electronic spectra of phthalocyanine derivatives and pyrromethene dye molecules doped into superfluid helium droplets have been investigated. Together with previous studies on anthracene derivatives [J. Chem. Phys.2010, 133, 114505] and 3-hydroxyflavone [J. Chem. Phys.2009, 131, 194307], the line shapes vary between two limiting cases, namely, sharp Lorentzians and nonresolved vibrational fine structure. All different spectral signatures are initiated by the same effect, namely, the change of the electron density distribution initiated by the electronic excitation. This change can be quantified by the difference of the electrostatic moments of the molecule in the electronic ground state and the corresponding Franck–Condon point in the excited state. According to the experimental data, electronic spectroscopy suffers from drastic line broadening when accompanied by significant changes of the charge distribution, in particular, changes of the dipole moment. Vice versa, the vibrational fine structure in electronic spectra of molecules doped into helium droplets is highly sensitive to changes of the electron density distribution. KW - Helium nanodroplets KW - Anthracene KW - Electronic spectroscopy Y1 - 2011 IS - 115 ER - TY - JOUR A1 - Lehnig, R. A1 - Pentlehner, Dominik A1 - Vdovin, A. A1 - Dick, B. A1 - Slenczka, Alkwin T1 - Photochemistry of 3-hydroxyflavone inside superfluid helium nanodroplets JF - The Journal of Chemical Physics N2 - 3-hydroxyflavone is a prototype system for excited state intramolecular proton transfer which is one step of a closed loop photocycle. It was intensively studied for the bare molecule and for the influence of solvents. In the present paper this photocycle is investigated for 3-hydroxyflavone and some hydrated complexes when doped into superfluid helium droplets by the combined measurement of fluorescence excitation spectra and dispersed emission spectra. Significant discrepancies in the proton transfer behavior to gas phase experiments provide evidence for the presence of different complex configurations of the hydrated complexes in helium droplets. Moreover, for bare 3-hydroxyflavone and its hydrated complexes the proton transfer appears to be promoted by the helium environment. KW - Helium nanodroplets KW - Atomic and molecular spectra KW - Photochemistry Y1 - 2009 IS - 131 ER -