Laboratory infrared spectroscopy of gaseous negatively charged polyaromatic hydrocarbons
- Radboud University Nijmegen, Institute for Molecules and Materials, FELIX Facility, Toernooiveld 7, 6525-ED Nijmegen (Netherlands)
Based largely on infrared spectroscopic evidence, polycyclic aromatic hydrocarbon (PAH) molecules are now widely accepted to occur abundantly in the interstellar medium. Laboratory infrared spectra have been obtained for a large variety of neutral and cationic PAHs, but data for anionic PAHs are scarce. Nonetheless, in regions with relatively high electron densities and low UV photon fluxes, PAHs have been suggested to occur predominantly as negatively charged ions (anions), having substantial influence on cloud chemistry. While some matrix spectra have been reported for radical anion PAHs, no data is available for even-electron anions, which are more stable against electron detachment. Here we present the first laboratory infrared spectra of deprotonated PAHs ([PAH-H]{sup –}) in the wavelength ranges between 6 and 16 μm and around 3 μm. Wavelength-dependent infrared multiple-photon electron detachment is employed to obtain spectra for deprotonated naphthalene, anthracene, and pyrene in the gas phase. Spectra are compared with theoretical spectra computed at the density functional theory level. We show that the relative band intensities in different ranges of the IR spectrum deviate significantly from those of neutral and positively charged PAHs, and moreover from those of radical anion PAHs. These relative band intensities are, however, well reproduced by theory. An analysis of the frontier molecular orbitals of the even- and odd-electron anions reveals a high degree of charge localization in the deprotonated systems, qualitatively explaining the observed differences and suggesting unusually high electric dipole moments for this class of PAH molecules.
- OSTI ID:
- 22356738
- Journal Information:
- Astrophysical Journal, Vol. 787, Issue 2; Other Information: Country of input: International Atomic Energy Agency (IAEA); ISSN 0004-637X
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
79 ASTROPHYSICS
COSMOLOGY AND ASTRONOMY
ABSORPTION SPECTROSCOPY
ANTHRACENE
COMPARATIVE EVALUATIONS
DENSITY FUNCTIONAL METHOD
ELECTRIC DIPOLE MOMENTS
ELECTRON DENSITY
ELECTRON DETACHMENT
INFRARED SPECTRA
NAPHTHALENE
PHOTONS
POLYCYCLIC AROMATIC HYDROCARBONS
PYRENE
WAVELENGTHS