PRESSURE SHIFTS AND ELECTRON-SCATTERING LENGTHS IN ATOMIC AND MOLECULAR GASES

Photoabsorption or photoionization spectra of CH3I are discussed as a function of perturber pressure for 11 different binary gas mixtures consisting of CH3I and each one of 11 different gaseous perturbers. Five of the perturbers were rare gases and six were nondipolar molecules. The energy shifts of CH3I Rydberg states become independent of n, the principal quantum number, for n greater-than-or-equal-to 10. The energy shifts for n greater-than-or-equal-to 10 vary in a linear fashion with perturber number density. The electron scattering lengths for the perturbers are extracted from the shifts using Fermi theory in which the polarization term is that of Alekseev and Sobel'man. These scattering lengths are compared with those from swarm and time-of-flight experiments. It is found that the uncorrected shift scattering lengths correspond to the zero energy or near-zero energy scattering lengths obtained from extrapolated swarm and time-of-flight data. It is found that plots of scattering length vs polarizability alpha (alphaBAR for molecules) define two linearities, one for the rare gases and one for molecules, CO2 being an exception to the latter linearity (presumably because of its large quadrupole moment). For a given polarizability, it is also found that molecules exhibit a larger scattering length than the rare gases. These results are discussed and consequences for scattering cross sections are elaborated.