Abstract
It is shown that measurements of fluorescence polarization from excited-state molecular photoions directly probe the symmetry signatures and synamical properties of autoionization resonances. To demonstrate this relationship, the excitation wavelength dependence of CO2+A2Πu→X2πg fluorescence polarization was measured following 1Πu photoionization of CO2. The resulting fluorescence polarization spectrum showed extensive autoionization structure that is reproduced well by a simple model which averages resonant and nonresonant ionization contributions to obtain a resultant polarization spectrum. Implications regarding CO2 spectral assignments are discussed. Moreover, the measurement appears to be a generally useful complement to existing probes of molecular autoionization. (AIP)
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