B21(Σu+1) excited state decay dynamics in CS2. Townsend, D., Satzger, H., Ejdrup, T., Lee, A. M. D., Stapelfeldt, H., & Stolow, A. The Journal of Chemical Physics, 125(23):234302, December, 2006. Publisher: American Institute of Physics
Paper doi abstract bibtex The authors report time resolved photoelectron spectra of the B21(Σu+1) state of CS2 at pump wavelengths in the region of 200nm. 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 (τ\textless50fs), in addition to a longer lived channel (τ∼350–650fs) 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 B21(Σu+1) state may decay to form either S(D1) or S(P3) 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 superp...
@article{Townsend2006a,
title = {B21(Σu+1) excited state decay dynamics in {CS2}},
volume = {125},
issn = {0021-9606},
url = {http://aip.scitation.org/doi/10.1063/1.2403137},
doi = {10.1063/1.2403137},
abstract = {The authors report time resolved photoelectron spectra of the B21(Σu+1) state of CS2 at pump wavelengths in the region of 200nm. 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 (τ{\textless}50fs), in addition to a longer lived channel (τ∼350–650fs) 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 B21(Σu+1) state may decay to form either S(D1) or S(P3) 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 superp...},
number = {23},
urldate = {2017-11-25},
journal = {The Journal of Chemical Physics},
author = {Townsend, Dave and Satzger, Helmut and Ejdrup, Tine and Lee, Anthony M. D. and Stapelfeldt, Henrik and Stolow, Albert},
month = dec,
year = {2006},
note = {Publisher: American Institute of Physics},
keywords = {\#nosource, carbon compounds, molecule-photon collisions, photoelectron spectra, photoionisation, predissociation, spin-orbit interactions, time resolved spectra, triplet state},
pages = {234302},
}
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