1B2(1Σu+) excited state decay dynamics in CS2

  1. Get@NRC: 1B2(1Σu+) excited state decay dynamics in CS2 (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1063/1.2403137
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Journal titleThe Journal Of Chemical Physics
Pages234302-1234302-10; # of pages: 10
Subjectcarbon compounds; molecule-photon collisions; photoelectron spectra; photoionisation; predissociation; spin-orbit interactions; time resolved spectra; triplet state
AbstractThe authors report time resolved photoelectron spectra of the 1B2 (1Σu+) state of CS2 at pump wavelengths in the region of 200 nm. In contrast to previous studies, the authors find that the predissociation dynamics is not well described by a single exponential decay. Biexponential modeling of the authors' data reveals a rapid decay pathway (tau<50 fs), in addition to a longer lived channel (τ ∼ 350-650 fs) that displays a marked change in apparent lifetime when the polarization of the pump laser is rotated with respect to that of the probe. Since the initially populated 1B2(1Σu+) state may decay to form either S(1D) or S(3P) products (the latter produced via a spin-orbit induced crossing from a singlet to a triplet electronic surface), this lifetime observation may be rationalized in terms of changes in the relative ionization cross section of these singlet and triplet states of CS2 as a function of laser polarization geometry. The experimentally observed lifetime of the longer lived channel is therefore a superposition of these two pathways, both of which decay on very similar time scales.
Publication date
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
NPARC number12330126
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Record identifierfb7570e4-83a5-44b2-91f0-ba2183eb8029
Record created2009-09-10
Record modified2017-03-23
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