Electric Field Induced Perturbations in the B21←A11 Transition of Aniline

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Abstract
Electric field induced perturbations have been observed in the 0–0 band of the B21←A11 (π*← π ) transition in aniline. From analysis of this effect, we infer the existence of a second state 0.10 cm−1 away with vibronic symmetry B2. Combined with a reinterpretation of a previously observed Stark effect in aniline, we determine the dipole moment of the π*← π state to be 2.45± 0.10 D, and that of the perturbing state to be 6.0± 0.4 D. The transition moment between the two mutually perturbing states is 0.5± 0.4 D, and lies along the long in-plane molecular axis. Since the perturbing state has such a different dipole moment from either the ground or π*← π state, it is most likely a π*← n or σ ↔ π transition. Possible implications of this effect for intersystem crossing rates are discussed.