Mechanism of vibrational relaxation and intersystem crossing within excited ion-pair states of I2 |
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Institution: | (1) Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, Iceland;(2) Present address: Kavalerg?rden 1, 2920 Charlottenlund, Denmark;(3) Present address: Department of Chemistry, University of California, 95064 Santa Cruz, Ca, USA |
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Abstract: | Visible and ultraviolet fluorescence of I2, following excitation by ArF/193nm excimer laser pulses, was recorded for different pressures of argon buffer gas in a flow
system. Dispersed fluorescence spectra due to the transitionsD’(2g) → A’(2y andD(0
n
+
)→X0
g
+
) were analysed by inversion and spectral simulations. Thus vibrational distributions in the emitting states were obtained
as a function of pressure to determine the mechanism of relaxation to populate the lowest quantum levels of theD’ state, which are the emitting states in the iodine laser. Fast intersystem crossing is found to occur from initially populated
vibrational levels of theD state to other ion-pair states correlating with the ground state ions, followed by rapid relaxation, involving both direct
vibrational relaxation within individual states and intersystem crossing between states. |
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Keywords: | Vibrational relaxation excited ion-pair vibrational distributions spectral simulations intersystem crossing |
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