15 May 1998 Photodissociation dynamics of I3 - using femtosecond photoelectron spectroscopy
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Abstract
The photodissociation dynamics of gas phase I3 following 390 nm excitation are studied with femtosecond photoelectron spectroscopy. Both I and I2 photofragments are observed; the I2 exhibits coherent oscillations with a frequency corresponding to an average vibrational level ((upsilon) ) equals 67. The oscillations dephase by 4 ps and rephase by approximately 45 ps. This can be understood by considering the dynamics of a coherent superposition of vibrational states on the anharmonic I2 potential. Our results represent the first example of coherently produced photodissociation products undergoing dynamical rephasing. Also for the first time the gas phase frequency of ground state I3 is determined via a resonance impulsive stimulated Raman scattering process. Finally, the photoelectron spectrum of I3 yields the vertical detachment energy of I3 and the spacing between the first two electronic states of the neutral I3 molecule. The photodissociation dynamics of gas phase I3 differ considerably from those observed in condensed phase experiments.
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Martin T. Zanni, Martin T. Zanni, B. Jefferys Greenblatt, B. Jefferys Greenblatt, Alison V. Davis, Alison V. Davis, Daniel M. Neumark, Daniel M. Neumark, } "Photodissociation dynamics of I3 - using femtosecond photoelectron spectroscopy", Proc. SPIE 3271, Laser Techniques for State-Selected and State-to-State Chemistry IV, (15 May 1998); doi: 10.1117/12.308408; https://doi.org/10.1117/12.308408
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