Abstract
An alternative method is described for the measurement of absolute optical oscillator strengths (cross sections) for electronic excitation of free atoms and molecules throughout the discrete region of the valence-shell spectrum at high energy resolution (full width at half maximum of 0.048 eV). The technique, utilizing the virtual-photon field of a fast electron inelastically scattered at negligible momentum transfer, avoids many of the difficulties associated with the various direct optical techniques that have traditionally been used for absolute optical oscillator strength measurements. The method is also free of the bandwidth (line saturation) effects that can seriously limit the accuracy of photoabsorption cross-section measurements for discrete transitions of narrow linewidth obtained using the Beer-Lambert law [I0/I=exp(nlσp)]. Since the line-saturation effects are not widely appreciated and are only usually considered in the context of peak heights, a detailed analysis of this problem is presented, with consideration of the integrated cross section (oscillator strength) over the profile of each discrete peak.