Conventional Determination of Ionization Energies

1 Improved IE Accuracy from Data Post-Processing 

Numerous approaches have been published to improve the accuracy of IE data. However, the uncertainty of electron energy remains, causing the ionization efficiency curves not to directly approach zero at IE. Instead of being linear, they bend close to the ionization threshold and exponentially approximate zero. Even though the electron energy scale of the instrument has been properly calibrated against lEs of established standards such as noble gases or solvents, IE data obtained from direct readout of the curve have accuracies of 0.3 eV (Fig. 2.19a). 

To overcome the uncertainty of the actual onset of ionization, among several others, [80] the critical slope method has been developed. [25,81] It makes use of the fact that from theory realistic values of IE are expected at the position of the ionization efficiency curve where the slope of a semilog plot of the curve is 

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