Infrared spectroscopy of gas-phase polycyclic aromatic hydrocarbon cations in the 10-50 mu m spectral range

TitleInfrared spectroscopy of gas-phase polycyclic aromatic hydrocarbon cations in the 10-50 mu m spectral range
Publication TypeJournal Article
Year of Publication2011
AuthorsJ.M Bakker, B. Redlich, A.FG van der Meer, J. Oomens
JournalAstrophysical Journal
Volume741
Issue2
Pagination9
Date PublishedNov
Type of ArticleArticle
ISBN Number0004-637X
KeywordsCORONENE, ELECTRONIC-SPECTRA, EMISSION, FREQUENCIES, infrared: ISM, IONS, ISM: molecules, methods: laboratory, molecular data, molecular processes, NAPHTHALENE, PAH MOLECULES, PENTACENE, POLYAROMATIC HYDROCARBONS, SPITZER-SPACE-TELESCOPE
Abstract

The gas-phase infrared spectra of four polycyclic aromatic hydrocarbon (PAH) cations have been recorded in the 10-50 mu m (or 1000-200 cm(-1)) spectral range via IR multiple photon dissociation (IRMPD) spectroscopy. Ionized PAHs are formed by UV laser ionization in an effusive beam and subsequently irradiated with a single pulse of narrowband tunable infrared light produced by the Free-Electron Laser for IntraCavity Experiments FELICE. The ion population is then analyzed in a time-of-flight mass spectrometer. Upon resonance, dissociation is induced so that IR spectra can be recorded by monitoring either the depleted parent ion intensity or the appearance of fragment ions as a function of the wavelength. The intracavity IR fluence enables the recording of IRMPD spectra of strongly bound PAH cations in the hitherto inaccessible far-IR spectral range. Experimental spectra are presented for the radical cations of anthracene, tetracene, pentacene, and coronene. Spectra calculated with density functional theory at the B3LYP/6-311g(2df,2pd) level reproduce IR frequencies reasonably accurately in this spectral range when a uniform scaling factor of 0.94 over the complete 10-50 mu m spectral range is employed. We show that even vibrational modes with a calculated IR intensity lower than 1 km mol(-1) can be observed. For the catacondensed PAH cations we find CH out-of-plane bending vibrations involving four adjacent CH groups within a few wavenumbers of 733 cm(-1), closely matching the 13.6 mu m UIR band. For the larger systems, pentacene and coronene, we observe a continuous structureless background absorption above 400 cm(-1) which is attributed to the high density of IR dipole allowed combination modes for these systems.

URLhttp://stacks.iop.org/0004-637X/741/i=2/a=74
Division

GUTHz

Department

Moldyn

PID

d22ec028a7b17f825e5cee6afa506d5c

Alternate TitleAstrophys. J.
LabelOA

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