Can. J. Chem. 82 (2004) 1052-1060
Quantitative oscillator strengths for ionic fragmentation of C 1s and O 1s excited CO

A.C.O. Guerra, J.B. Maciel, C.C. Turci, R.C. Bilodeau, and A.P. Hitchcock

Received 5 December 2003. Published on the NRC Research Press Web site at on 14 September 2004.

Abstract - Ionic photofragmentation of carbon monoxide following carbon 1s and oxygen 1s excitation has been measured quantitatively with tuned synchrotron light and time-of-flight mass spectrometry using a Wiley–McLaren apparatus modified with an additional ion lens for improved quantitative performance. The sensitivity of the apparatus to kinetic energy and angular distribution effects has been characterized for selected lens settings through ion trajectory simulations and experimental measurements. Three distinct modes of the added lens have been identified (focus, defocus, and maximum). The focus mode has the least sensitivity to details of the angular and ion kinetic energy distribution and, therefore, is the best mode for measuring quantitative partial ion and ion-pair yields. The defocus mode has the most sensitivity to angular and kinetic energy distributions and, therefore, is the mode that provides the most information about the kinematics of photofragmentation. Branching ratios for ion and ion-pair production in all positive ion fragmentation channels were recorded from 280 to 330 eV (C 1s) and from 520 to 570 eV (O 1s) in the “focus” mode. Quantitative oscillator strengths were derived by combining these branching ratios with absolute total ion yield spectra. The results are compared to literature values.

Key words: CO, time-of-flight mass spectrometry, inner-shell excitation, quantitative oscillator strengths, cross sections.