Electronic Spectroscopy of Molecules in Superfluid Helium Nanodroplets: An Excellent Sensor for Intramolecular Charge Redistribution

Pentlehner, D. and Riechers, R. and Vdovin, A. and Poetzl, G. M. and Slenczka, A. (2011) Electronic Spectroscopy of Molecules in Superfluid Helium Nanodroplets: An Excellent Sensor for Intramolecular Charge Redistribution. JOURNAL OF PHYSICAL CHEMISTRY A, 115 (25). pp. 7034-7043. ISSN 1089-5639,

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Abstract

Electronic spectra of molecules doped into superfluid (4)He 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 on 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.

Item Type: Article
Uncontrolled Keywords: FREE-BASE PHTHALOCYANINE; FLUORESCENCE EXCITATION SPECTRUM; JET-COOLED 3-HYDROXYFLAVONE; STATE PROTON-TRANSFER; SUPERSONIC FREE JET; LIQUID-HELIUM; HE DROPLETS; CLUSTER; DYES; RELAXATION;
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry)
Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Alkwin Slenczka
Depositing User: Dr. Gernot Deinzer
Date Deposited: 09 Jun 2020 06:25
Last Modified: 09 Jun 2020 06:25
URI: https://pred.uni-regensburg.de/id/eprint/20642

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