Abstract
Abstract Electron affinities and electron attachment energies associated with the π* orbitals of several p-alkylanilines (alkyl = Me, Et, i-Pr, and t-Bu) have been determined in the gas phase by electron transmission spectroscopy and have been analyzed by ab initio molecular orbital calculations at the STO-3G and 6-31G levels of basis set. The results lead to the conclusions that (a) the 2A2 negative ion state in toluene lies below the 2B1 state, (b) the 2A2 state is stabilized in toluene relative to benzene by bonding overlap between the ortho carbon (C2(2pπ)) and the Me H(1s) orbitals in the LUMO, (c) the 2B1 state is stabilized on adding Me groups to toluene to form t-butylbenzene through reduced antibonding interactions between C1(2pπ) and Me C(2pπ) orbitals, and (d) the lowest resonance in t-butylbenzene is extensively overlapped with the second resonance and may involve strong mixing of the 2A2 and 2B1 states.
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