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Resonance-enhanced multiphoton ionization and fragmentation of molecular beams: NO, I2, benzene, and butadiene

J. Chem. Phys. 71, 1359 (1979); doi:10.1063/1.438436

Issue Date: 1 August 1979

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L. Zandee and R. B. Bernstein
Department of Chemistry, Columbia University, New York, New York 10027
Using the technique of laser ionization mass spectrometry, studies have been carried out of multiphoton ionization (MPI) and fragmentation of molecules under collision-free conditions. MPI spectra and mass fragmentation patterns are obtained via irradiation of isolated molecules by a pulsed, tunable dye laser focused down on a molecular beam traversing the ion-source region of a quadrupole mass filter. At each resonance, corresponding to m-photon ionization of an n-photon-excited intermediate state, the fragmentation pattern of the ions is measured. Resonance-enhanced MPI/mass spectra provide detailed information on the identity and relative abundances of the ionic fragments formed in the overall n+m photoionization process. From a knowledge of the appearance potentials of the various fragment ions, the minimum number of photons absorbed per molecule can be deduced. Increasing the laser pulse peak energy (or fluence) increases the average number of photons absorbed and thus the extent of fragmentation. However, even at the highest laser peak power densities used, the ionization (and fragmentation) remains extremely wavelength selective; the nonresonant contribution to the ionization is only a small fraction of the resonance-enhanced ion yields. Detailed experimental results on the 2+m photon ionization of benzene (the Johnson band, near 391 nm) are reported. Under strong focusing conditions, the most abundant ion is found to be C+, which implies the absorption of as many as 9 photons per molecule during the 6 ns pulse length of the laser. For I2, two different (n=2) bands were studied: for the Dalby system (near 372 nm), m=1 and 2, while for the Goodman band (near 585 nm), m=4. For trans-1,3-butadiene (near 387 nm), products requiring m=4 are observed. It is estimated that under the conditions of the present experiments ?10−4 of the beam molecules within the focal region are ionized by the laser pulse. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
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KEYWORDS and PACS

Keywords
PACS
  • 33.80.Eh
    Molecular spectra and interactions of molecules with photons Molecular photon processes Autoionization, photoionization, and photodetachment
  • 33.80.Kn
    Molecular spectra and interactions of molecules with photons Molecular photon processes Multiphoton processes
  • 34.50.Lf
    Atomic and molecular collision processes and interactions Inelastic scattering of atoms and molecules Chemical reactions, energy disposal, and angular distribution, as studied by atomic and molecular beams
  • 82.80.Ms
    Physical chemistry Chemical analysis and related physical methods of analysis Mass spectrometry
  • YEAR: 1979

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (41)
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