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Ultrafast vibrational dynamics in higher electronic excited states of iodine
Author(s) -
Liebers Jörg,
Scaria Abraham,
Materny Arnulf,
Kleinekathöfer Ulrich
Publication year - 2009
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2221
Subject(s) - atomic physics , ion , chemistry , excited state , ultrashort pulse , degenerate energy levels , four wave mixing , mixing (physics) , wavelength , molecular physics , nonlinear optics , physics , optics , laser , organic chemistry , quantum mechanics
By using a combination of an initial pump pulse and a degenerate four‐wave mixing (DFWM) process, we show that an interrogation of the vibrational dynamics occurring in high‐lying electronic states of molecules is possible. As a test case, the technique is applied to iodine in experiment and in simulation. The initial pump pulse is used to populate the B state of molecular iodine in the gas phase. By using an internal time delay in the subsequent DFWM process, which is resonant with the transition between the B state and a higher lying ion‐pair state, the vibrational dynamics of the B ( $^{3}\Pi_{\rm {u}}^+$ ) state as well as of the ion‐pair state could be observed. From the possible ion‐pair states, the states of even symmetry are investigated, which are accessible by a one‐photon transition from the B state. By a proper choice of the wavelengths used for the pump and DFWM beams, the dynamics of ion‐pair states belonging to two different tiers are monitored. Very good agreement between experimental and theoretical results is observed in most of the studied wavelength combinations. Copyright © 2009 John Wiley & Sons, Ltd.