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Photochemistry of naphthalene cluster ions (C{sub 10}H{sub 8}){sub n}{sup +}, n = 2-7. Formation of C{sub 11}H{sub 9}{sup +} ion via intervalence band excitation

Journal Article · · Journal of the American Chemical Society
;  [1]
  1. Univ. of Akron, OH (United States)

The photodissociation dynamics of naphthalene cluster ions, (C{sub 10}H{sub g}){sub n}{sup +} with n = 2-7, in the visible and near-IR wavelength regions have been probed by photoionization-photofragmentation time-of-flight mass spectroscopy. An intracluster reaction leading to production of a C{sub 11}H{sub 9}{sup +} ion is observed when the parent cluster ions are excited with near-IR photons, while only intramolecular fragmentation pathways occur following visible band excitation. The formation of C{sub 11}H{sub 9}{sup +}, which is assumed to possess the benzotropylium structure, is ascribed to a photochemical rearrangement of the dimer ion core produced in the parent clusters upon multiphoton excitation via the intervalence transition band. The intracluster reaction is observed only for parent cluster sizes n {>=} 4, which suggests that the dimer ion core must be surrounded by a solvent cage involving at least two neutral molecules. We propose that the existence of a dimer core structure plays an important role in the photochemistry that occurs subsequent to excitation into the intervalence transition band. 33 refs., 7 figs.

Sponsoring Organization:
USDOE
DOE Contract Number:
FG02-89ER14024
OSTI ID:
81290
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 13 Vol. 117; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English