Electric Field Induced Perturbations in the1B2larr;1A1Transition of Aniline

摘要

Electric field induced perturbations have been observed in the 0ndash;0 band of the1B2larr;1A1lpar;pgr;*larr; pgr; rpar;transition in aniline. From analysis of this effect, we infer the existence of a second state 0.10 cmminus;1away with vibronic symmetryB2. Combined with a reinterpretation of a previously observed Stark effect in aniline, we determine the dipole moment of thepgr;*larr; pgr;state to be2.45plusmn; 0.10thinsp;D, and that of the perturbing state to be6.0plusmn; 0.4thinsp;D. The transition moment between the two mutually perturbing states is0.5plusmn; 0.4thinsp;D, and lies along the long inhyphen;plane molecular axis. Since the perturbing state has such a different dipole moment from either the ground orpgr;*larr; pgr;state, it is most likely apgr;*larr; norsgr; harr; pgr;transition. Possible implications of this effect for intersystem crossing rates are discussed.