Abstract
We study the influence of an applied electric field on the fully resolved electronic spectra of aniline (AN), benzonitrile (BN), and 4-aminobenzonitrile (ABN) in the gas phase. Using these data, we test the commonly held but rarely proven assumption that the total dipole moment of a polyatomic molecule is the vector sum of bond dipole moments, localized in different parts of the molecule. We find that μ a (ABN)≈ μ a (AN)+ μ a (BN) in the excited S 1 state, but not in the ground S 0 state. Possible reasons for this non-additivity are discussed.
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