DOI | Resolve DOI: https://doi.org/10.1063/1.2403137 |
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Author | Search for: Townsend, Dave1; Search for: Satzger, Helmut1; Search for: Ejdrup, Tine; Search for: Lee, Anthony M. D.1; Search for: Stapelfeldt, Henrik; Search for: Stolow, Albert1 |
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Affiliation | - National Research Council of Canada. NRC Steacie Institute for Molecular Sciences
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Format | Text, Article |
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Subject | carbon compounds; molecule-photon collisions; photoelectron spectra; photoionisation; predissociation; spin-orbit interactions; time resolved spectra; triplet state |
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Abstract | The 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. |
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Publication date | 2006-12-18 |
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In | |
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Language | English |
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Peer reviewed | Yes |
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NPARC number | 12330126 |
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Export citation | Export as RIS |
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Record identifier | fb7570e4-83a5-44b2-91f0-ba2183eb8029 |
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Record created | 2009-09-10 |
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Record modified | 2020-04-22 |
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