RYDBERG COMPLEXES OF METHYL-CHLORIDE CHARACTERIZED BY (2-ENHANCED MULTIPHOTON IONIZATION(1) AND (3+1) RESONANCE)

The two- and three-photon resonant spectra of CH3Cl have been recorded in the region of the lower Rydberg states. Assignments are made for n umerous electronic and vibrational bands related to the first two memb ers of the s, p, and d Rydberg series in CH3Cl, extending or revising the assignments of previous workers. Comparisons of two- and three-pho ton spectra and polarization effects show strong contrast and reveal t he varying degrees of atomic behavior in the six electronic states stu died. The orbital angular momentum quantum number of the Rydberg state is shown to have a greater influence on the degree of penetration and consequent deviation from hydrogen-like orbital character than the ma gnitude of the principal quantum number.