Abstract
Pulsed field ionization zero kinetic energy (PFI-ZEKE) photoelectron spectra were measured for jet-cooled o-, m-, and p-methylanisoles for the first time. The low-frequency bands observed at around the origin band in the spectra were assigned to the methyl internal rotational bands of the cations. The potential curves and the Franck–Condon factors for the methyl internal rotational motion were calculated by the one-dimensional free-rotor approximation. The potential barrier height was found to change drastically on ionization, suggesting that the electronic structure should mainly affect the potential barrier of the methyl internal rotation.
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