Molecules excited to regions of high state density are not deflected by an inhomogeneous electric field

Fraser, Gerald T.; Pate, Brooks H.
February 1993
Journal of Chemical Physics;2/1/1993, Vol. 98 Issue 3, p2477
Academic Journal
Conclusive experimental evidence is presented that molecules excited to a single ro-vibrational eigenstate in a high density-of-states region are not deflected by an inhomogeneous electric field. The onset of nondeflection behavior occurs in the same density of states region as has been found for the onset of intramolecular vibrational energy redistribution IVR (about 10 vibrational states/cm-1). By using large polyatomic molecules, where the hydride stretch fundamentals occur in this range of state density, the nondeflection behavior can be studied. However, the results are generally applicable to the dynamics of smaller molecules at higher levels of excitation. Thus, the observed nondeflection in our experiments is expected to be a general phenomenon associated with highly vibrationally excited molecules. In addition, it is shown how the nondeflection characteristics of these systems can be exploited experimentally to obtain spectra with increased sensitivity.


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