TY - JOUR A1 - Pentlehner, Dominik A1 - Greil, Ch. A1 - Dick, B. A1 - Slenczka, Alkwin T1 - Line broadening in electronic spectra of anthracene derivatives inside superfluid helium nanodroplets JF - The Journal of Chemical Physics N2 - Electronic spectroscopy of molecules profits greatly from superfluid helium droplets serving as a gentle cryogenic matrix. Characteristic features of electronic spectra in helium droplets are a solvent shift, phonon wings, and in rare cases a splitting of zero phonon lines. For the majority of molecules investigated so far in helium droplets the vibrational fine structure in electronic spectra resembles what was observed in a supersonic jet. The electronic spectra of three methylated anthracene derivatives and one phenylated anthracene discussed in this paper reveal remarkable effects in the vibrational fine structure due to solvation in helium droplets. For all four compounds the vibrational frequencies were almost not affected by the helium environment. However, if the electronic excitation is accompanied by nuclear rearrangement, the spectra showed remarkable line broadening in helium droplets. This is the case for 2-methylanthracene and 9-phenylanthracene. The corresponding line shape was of Lorentzian type and, thus, attributed to damping of the excited system by the helium environment. According to the linewidth the damping time constant was determined to be about 0.3 ps in the case of 2-methylanthracene and 0.1 ps for 9-phenylanthracene. KW - Helium nanodroplets KW - Anthracene derivates KW - Electronic spectroscopy Y1 - 2010 IS - 133 ER - TY - JOUR A1 - Stromeck-Faderl, A. A1 - Pentlehner, Dominik A1 - Kensy, U. A1 - Dick, B. T1 - High-resolution electronic spectroscopy of the BODIPY chromophore in supersonic beam and superfluid helium droplets JF - CHEM-PHYS-CHEM, Special Issue: Laser Chemistry and Spectroscopy N2 - We present the fluorescence excitation and dispersed emission spectra of the parent compound of the boron dipyrromethene (BODIPY) dye class measured in a supersonic beam and isolated in superfluid helium nanodroplets. The gas‐phase spectrum of the isolated molecules displays many low‐frequency transitions that are assigned to a symmetry‐breaking mode with a strongly nonharmonic potential, presumably the out‐of‐plane wagging mode of the BF2 group. The data are in good agreement with transition energies and Franck–Condon factors calculated for a double minimum potential in the upper electronic state. The corresponding transitions do not appear in the helium droplet. This is explained with the quasi‐rigid first layer of helium atoms attached to the dopant molecule by van der Waals forces. The spectral characteristics are those of a cyanine dye rather than that of an aromatic chromophore. KW - Helium nanodroplets KW - Electronic spectroscopy KW - BODIPY Chromophore Y1 - 2011 IS - 12 ER - 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 - Premke, Tobias A1 - Wirths, Eva-Maria A1 - Pentlehner, Dominik A1 - Riechers, Ricarda A1 - Lehnig, Rudolf A1 - Vdovin, Alexander A1 - Slenczka, Alkwin T1 - Microsolvation of molecules in superfluid helium nanodroplets revealed by means of electronic spectroscopy JF - Frontiers in Chemistry N2 - 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. KW - Microsolvation of molecules KW - Helium nanodroplets KW - Electronic spectroscopy Y1 - 2014 VL - 2014 IS - 2 ER -