Electronic symmetries, dipole moments, and polarizabilities of molecules in Rydberg states determined from electric-field effects on absorption spectra

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Abstract
The effects of intense electric fields (∼ 2×105 V cm−1) on the gas‐phase, ultraviolet absorption spectra of acetone and dimethylsulfide are investigated for the purpose of determining the changes in the electric dipole moments and polarizabilities and the transition polarizations corresponding to three bands assigned to Rydberg transitions. The bands investigated are the 1954 Å band of acetone assigned to the 3s←n (1B2←1A1) Rydberg transition and the 1959 and 2284 Å bands of dimethylsulfide assigned to the 4p←n (1A1←1A1) and 4s←n (1B1←1A1) Rydberg transitions, respectively. Interpretation of the results revealed that, for the transition in acetone and the 4p←n and 4s←n transitions in dimethylsulfide, the dipole moments are reduced from the ground‐state values by 0.48±0.02 D, 0.47±0.03 D, and 0.42±0.04 D, respectively, and the mean polarizabilities are increased by 17.3±1.5×10−24 cm3, 11.7±1.3×10−24 cm3, and 9.3±2.0×10−24 cm3, respectively. The transition polarizations were all found to be in agreement with their particular Rydberg assignments. Derivations of the mathematical equations necessary for the interpretation of the experimental data are presented.