"Electronic continua in time-resolved photoelectron spectroscopy. II. Corresponding ionization correlations"M. Schmitt, S. Lochbrunner, J. P. Shaffer, J. J. Larsen, M. Z. Zgierski, and A. Stolow
J. Chem. Phys. 114 (2001), 1206-1213
We investigate further the role of ion electronic continua in time-resolved photoelectron spectroscopic measurements of ultrafast nonadiabatic coupling. In the preceding paper [Blanchet,Zgierski, and Stolow, J. Chem.
Phys. 114, 1194 (2000)], the limiting case of complementary ionization correlations permitted a disentangling of electronic from vibrational dynamics. Here we examine the other limiting case in which the
nonadiabatically coupled sates (e.g., S 2 and S 1 ) correlations correspond to the same ionic continua, presumably an unfavorable case. We use ultrafast internal conversion in the polyaromatic hydrocarbons
phenanthrene and naphthalene as examples. In this situation, the geometry changes (displacements) upon nonadiabatic crossing and upon ionization will strongly affect the ability to disentangle electronic from
vibrational dynamics. Particularly, phenanthrene and naphthalene are both very rigid molecules and have small displacements upon internal conversion and ionization, still allowing for direct monitoring of the S 2 state
internal conversion rate.
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