Fluorescence Polarization Studies: A Global View of Molecular Photoionization Dynamics Over an Extended Energy Range.

The experimental technique of measuring the degree of polarization of the fluorescence from electronically excited molecular ions is used to determine the alignment of N\sb2, CO and N\sb2O photoions over an extended range of excitation energy. The polarization of \rm CO\sp+(B\sp2\Sigma\sp+\to\ X\sp2\Sigma\sp+),\ N\sb2\sp+(B\sp2\Sigma\sb{u}\sp+\ \to \ X\sp2\Sigma\sb{g}\sp+), and \rm N\sb2O\sp+\ (A\sp2\Sigma\sp+\ \to\ X\sp2\Pi) fluorescence over a 200 eV photon energy range is used to interpret the oscillator strength distributions for normally unresolved degenerate ionization channels. The results show the influence of a CO $4\sigma\to k\sigma$ shape resonance clearly, and agreement between theory and experiment is excellent. The N\sb2O experimental results indicate evidence of a $7\sigma\to k\sigma$ shape resonance near ionization threshold. Agreement between the theoretical calculations and experiment are less satisfactory for N\sb2. This behavior is somewhat surprising, as previous rotationally resolved fluorescence experiments have shown excellent agreement between theory and experiment. This comparison helps to illustrate the complementarity of alignment studies relative to alternative probes of ionization. For both N\sb2 and CO, the data indicate that the photoions retain significant alignment even at high energies, though this is not true in the case of N\sb2O. The results demonstrate that even well above threshold the spectral dependence of the alignment (i.e., polarization) is very sensitive to the molecular environment for photoejection. Such behavior provides useful insight into fundamental scattering phenomena in chemical physics

Photoion Alignment: Chemical Signatures 200 eV above Threshold

We present results of experiment and theory for the alignment of CO^+(B^2Σ^+) and N_2^+(B^2Σ^+_u) photoions over an extended energy range (0 ≤ E_k ≤ 210 eV for CO and 0 ≤ E_k ≤ 250 eV for N_2). The polarization of CO^+(B^2Σ^+ → X^2Σ^+) and N_2^+(B^2Σ^+ → X^2Σ^+_g) fluorescence is used to interpret the oscillator strength distributions for normally unresolved degenerate ionization channels. The results show the influence of a CO 4σ → kσ shape resonance clearly and agreement between theory and experiment is excellent. However, agreement between the calculated and measured values is less satisfactory for N_2. This behavior is somewhat surprising, as previous rotationally resolved fluorescence experiments have shown excellent agreement between theory and experiment. This comparison helps to illustrate the complementarity of alignment studies relative to alternative probes of ionization. For both N_2 and CO, the data indicate that the photoions retain significant alignment even at high energies. The results demonstrate that even well above threshold the spectral dependence of the alignment (i.e., polarization) is very sensitive to the molecular environment for photoejection. Such behavior provides useful insight into fundamental scattering phenomena in chemical physics