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Unimolecular dissociation rate constants: Chlorobenzene cations revisited by using a new method

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100372a058· OSTI ID:6439737
; ;  [1]
  1. Pennsylvania State Univ., University Park (USA)

Unimolecular dissociation rates of metastable molecular ions formed at the laser focus of a time-of-flight mass spectrometer (TOFMS) have been determined by measuring the relative concentrations of parent metastable ions and the daughter fragment ions as a function of their retained kinetic energies upon dissociation. This is accomplished by the use of a simple one-stage ion mirror/energy analyzer. For a given reflection potential on the ion mirror, only those ions with a kinetic energy equal to or less than the reflection potential are detected. In this way, the relative concentrations of the parent and daughter ions as a function of their position of dissociation in the time-of-flight (TOF) lens can be measured, and consequently the dissociation lifetime can be derived. This technique has been applied to measuring the unimolecular dissociation rate of chlorobenzene ion (C{sub 6}H{sub 5}Cl{sup +}) in the three-photon energy range of 13.64-13.92 eV through resonance-enhanced two-photon state-selected ionization of chlorobenzene in a supersonic molecular jet.

DOE Contract Number:
FG02-88ER60648
OSTI ID:
6439737
Journal Information:
Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:9; ISSN 0022-3654; ISSN JPCHA
Country of Publication:
United States
Language:
English