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 - Slenczka, Alkwin A1 - Pentlehner, Dominik T1 - Electronic spectroscopy of 9,10-dichloroanthracene inside helium droplets JF - The Journal of Chemical Physics N2 - The spectroscopy of molecules doped into superfluid helium droplets provides information on both, the dopant molecule and the helium environment. Electronic spectra of 9,10-dichloroanthracene in helium droplets are presented and compared with corresponding gas phase spectra to unravel the influence of the helium environment. The combined investigation of fluorescence excitation and dispersed emission provides information on dynamic processes in addition to energetic conditions. For vibronic states, the helium induced decay channels dominate over all intramolecular channels that contribute to the gas phase behavior. In addition to the triplet splitting caused by the Cl isotopes, a fine structure resolved for all transitions in the fluorescence excitation spectrum was found, which is the signature of microsolvation of this compound in helium droplets. This fine structure is identified as a single pure molecular transition accompanied by a sharply structured phonon wing. The corresponding fine structure measured for bare anthracene shows remarkable differences. KW - Helium nanodroplets KW - Emission spectroscopy KW - Doppler effect Y1 - 2013 IS - 138 ER - TY - JOUR A1 - Riechers, Rudolf A1 - Pentlehner, Dominik A1 - Slenczka, Alkwin T1 - Microsolvation in superfluid helium droplets studied by the electronic spectra of six porphyrin derivatives and one chlorine compound JF - The Journal of Chemical Physics N2 - After almost two decades of high resolution molecular spectroscopy in superfluid helium droplets, the understanding of microsolvation is still the subject of intense experimental and theoretical research. According to the published spectroscopic work including microwave, infrared, and electronic spectroscopy, the latter appears to be particularly promising to study microsolvation because of the appearance of pure molecular transitions and spectrally separated phonon wings. Instead of studying the very details of the influence of the helium environment for one particular dopant molecule as previously done for phthalocyanine, the present study compares electronic spectra of a series of non-polar porphyrin derivatives when doped into helium droplets consisting of 104–105 helium atoms. Thereby, we focus on the helium-induced fine structure, as revealed most clearly at the corresponding electronic origin. The interpretation and the assignment of particular features obtained in the fluorescence excitation spectra are based on additional investigations of dispersed emission spectra and of the saturation behavior. Besides many dopant-specific results, the experimental study provides strong evidence for a particular triple peak feature representing the characteristic signature of helium solvation for all seven related dopant species. KW - Superfluid helium droplets KW - Porphyrin derivatives KW - Chlorine compound Y1 - 2013 IS - 138 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 - TY - JOUR A1 - Pentlehner, Dominik A1 - Slenczka, Alkwin T1 - Helium induced fine structure in the electronic spectra of anthracene derivatives doped into superfluid helium nanodroplets JF - The Journal of Chemical Physics N2 - Electronic spectra of organic molecules doped into superfluid helium nanodroplets show characteristic features induced by the helium environment. Besides a solvent induced shift of the electronic transition frequency, in many cases, a spectral fine structure can be resolved for electronic and vibronic transitions which goes beyond the expected feature of a zero phonon line accompanied by a phonon wing as known from matrix isolation spectroscopy. The spectral shape of the zero phonon line and the helium induced phonon wing depends strongly on the dopant species. Phonon wings, for example, are reported ranging from single or multiple sharp transitions to broad (Δν > 100 cm−1) diffuse signals. Despite the large number of example spectra in the literature, a quantitative understanding of the helium induced fine structure of the zero phonon line and the phonon wing is missing. Our approach is a systematic investigation of related molecular compounds, which may help to shed light on this key feature of microsolvation in superfluid helium droplets. This paper is part of a comparative study of the helium induced fine structure observed in electronic spectra of anthracene derivatives with particular emphasis on a spectrally sharp multiplet splitting at the electronic origin. In addition to previously discussed species, 9-cyanoanthracene and 9-chloroanthracene will be presented in this study for the first time. KW - Superfluid helium nanodroplets KW - Anthracene derivates Y1 - 2015 IS - 142 ER - TY - JOUR A1 - Pentlehner, Dominik A1 - Slenczka, Alkwin T1 - Microsolvation of anthracene inside superfluid helium nanodroplets JF - Journal of Molecular Physics, Special Issue: Dudley Herschbach Festschrift N2 - This article reports on the microsolvation of anthracene in superfluid helium nanodroplets as revealed by electronic spectroscopy. Among the polyacene molecules benzene, naphthalene, anthracene, tetracene and pentacene only anthracene and tetracene have been found to exhibit multiplet splitting of the electronic and vibronic transitions which can not be explained by a rotational fine structure. The experimental approach for the investigation of the multiplet is the combined investigation of the fluorescence excitation spectrum and dispersed emission spectra. New experimental data are presented on the microsolvation of anthracene in helium droplets. A detailed analysis of the anthracene data will be contrasted to corresponding data on tetracene. These data together with those reported for benzene, naphthalene and pentacene might serve to test and develop theoretical models which are needed to understand microsolvation of single molecules in superfluid helium droplets. KW - Helium nanodroplets KW - Anthracene KW - Tetracene KW - Micro-Solvation Y1 - 2012 IS - 110 ER - TY - JOUR A1 - Pentlehner, Dominik A1 - Riechers, Ricarda A1 - Dick, B. A1 - Slenczka, Alkwin A1 - Even, U. A1 - Lavie, N. A1 - Brown, R. A1 - Luria, K. T1 - Rapidly pulsed helium droplet source JF - Review of scientific instruments N2 - A pulsed valve connected to a closed-cycle cryostat was optimized for producing helium droplets. The pulsed droplet beam appeared with a bimodal size distribution. The leading part of the pulse consists of droplets suitable for doping with molecules. The average size of this part can be varied between 104 and 106 helium atoms, and the width of the distribution is smaller as compared to a continuous-flow droplet source. The system has been tested in a single pulse mode and at repetition rates of up to 500 Hz with almost constant intensity. The droplet density was found to be increased by more than an order of magnitude as compared to a continuous-flow droplet source. KW - Scientific instruments KW - Helium nanodroplets KW - Superfluids Y1 - 2009 IS - 80 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 - Pentlehner, Dominik A1 - Nielsen, Jens H. A1 - Slenczka, Alkwin A1 - Mølmer, Klaus A1 - Stapelfeldt, Henrik T1 - Impulsive Laser Induced Alignment of Molecules Dissolved in Helium Nanodroplets JF - Physical Review Letters N2 - We show that a 450 fs nonresonant, moderately intense, linearly polarized laser pulse can induce field-free molecular axis alignment of methyliodide (CH3I) molecules dissolved in a helium nanodroplet. Time-resolved measurements reveal rotational dynamics much slower than that of isolated molecules and absence of the sharp transient alignment recurrences characteristic of gas phase molecules. Our results presage a range of new opportunities for exploring both molecular dynamics in a dissipative environment and the properties of He nanodroplets. KW - Helium nanodroplets KW - mpulsive Laser Induced Alignment Y1 - 2013 IS - 110 ER - TY - JOUR A1 - Pentlehner, Dominik A1 - Nielsen, Jens H. A1 - Christiansen, Lars A1 - Slenczka, Alkwin A1 - Stapelfeldt, Henrik T1 - Laser Induced Adiabatic Alignment of Molecules Dissolved in Helium Nanodroplets JF - Physical Review A N2 - A moderately intense, nonresonant, linearly polarized nanosecond laser pulse is used to induce one-dimensional (1D) adiabatic alignment of 1,4 diiodobenzene (C6H4I2), iodobenzene (C6H5I), and methyliodide (CH3I) molecules dissolved in helium nanodroplets. The alignment sharpens as the laser intensity is increased, similar to the behavior in gas phase. For diiodobenzene the highest degree of alignment, ⟨cos2θ2D⟩=0.90, is essentially identical to the value obtained for isolated molecules in a supersonic beam, whereas the highest degrees of alignment for iodobenzene and for methyliodide in helium droplets fall below the values obtained for isolated molecules. We believe this is due to the deviation from axial recoil in the Coulomb explosion process that probes the alignment of the molecules in the He droplets. KW - Helium nanodroplets KW - Linearly polarized nanosecond laser pulse Y1 - 2013 IS - 87 ER -