Possible mechanisms of RG+ production from NO–RG photolysis (see text for details). (Left) Photo-induced charge transfer (PICT) dissociative ionization. (Center) PICT dissociation of the NO+–Xe molecular ion. (Right) Two-photon dissociation leading to Xe* production. Photoexcitations are represented by upward pointing arrows (blue), electron kinetic energy (eke) by downward pointing arrows (red) and total kinetic energy release (nKER) by double headed arrows. Relative energies at which PICT occurs are shown with dashed horizontal lines (green). The approximate equilibrium geometries of NO–RG electronic states are displayed in the left hand panel.
REMPI spectra observed for NO, NO–Ar, Kr, and NO–Kr in the region of the NO–RG – transition (44 150–44 375 cm−1). Progressions observed in [NO–RG]+ (and Kr+) species arise due to excitation of the state NO–RG local mode (Ref. 10).
REMPI spectra observed for Xe and NO–Xe in the 44 125–44 375 cm−1 region. Peaks marked with an asterisk (*) arise from (2+1) REMPI of Xe via the 5p5(2 P°3/2)7p2[5/2]2–5p6(1 S 0) and 5p5(2 P°3/2)7p2[3/2]2–5p6(1 S 0) atomic transitions (Ref. 25).
(Top right) Reconstructed Kr+ image recorded following Kr·NO photolysis via the – transition at 44 260.5 cm−1. The electric field vector (E) of the photolysis laser is vertical with respect to the plotted image. (Top left) nKER spectrum extracted from the Kr+ image shown. (Bottom left) Simulated nKER spectrum for NO(X 2Π) cofragment produced with 2400 cm−1 (see text for details).
nKER spectra extracted from Kr+ images acquired following NO–Kr photolysis via the four members of the – band system. = 44 297.9 cm−1, = 44 260.5 cm−1, = 44 230.1 cm−1, and = 44 202.0 cm−1. The experimental data are plotted as black squares, while the solid curve (red) shows a 5-point smooth of the data.
nKER spectrum extracted from the Xe+ image recorded following photolysis of NO–Xe at 44 303.1 cm−1. Weaker product channels observed at ∼20 000 cm−1 are due to photolysis of Xe2 at the two-photon level. The electric field vector (E) of the photolysis laser is vertical with respect to the plotted image.
nKER spectrum of the Xe+ photofragment produced via photolysis of NO–Xe at various excitation wavenumbers with the – transition. Experimental data are plotted as black squares, while fitted Gaussian peaks are plotted as dashed blue lines. A sum of the Gaussian curves is plotted as a thick red line. The separations between the fitted Gaussian curve peak maxima corresponds to vibrational intervals in the NO cofragment.
Possible pathways and energetics for production of RG+ following photolysis of NO–RG.
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