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- W2023781968 abstract "Vibrational structure associated with the 2940-Å band system of aniline vapor has been analyzed in some detail, and results are included for the −d2, −d5, and −d7 isotopes. It is shown that the ω(NH2) vibration is strongly anharmonic in the ground state, having the small-large alternation of quanta characteristic of a vibration occurring in a double-minimum potential. The data are consistent with an angle of about 46° between the ring-to-N bond and the NH2 plane in the electronic ground state. The same vibration is not harmonic in the upper electronic state, though its anharmonic character is less strongly marked there than in the ground state. The data for the upper state are compatible with a double-minimum potential having a very small maximum for the all-coplanar configuration, but the evidence is not conclusive. All that can be said definitely is that ∂3V(q)∂q3 ≠ 0 for a considerable range of q to either side of q = 0. The term quasiplanar is proposed to cover this situation, a few other examples of which can be found in the literature. A complete classification of the vibronic sublevels of aniline is accomplished using a group G8 of order eight; but the torsional splittings are not resolved in the electronic spectrum so that the practically useful group is G4, a sub-group of G8 . G4 is isomorphous with the point group C2v. The vibronic selection rules are discussed." @default.
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- W2023781968 date "1966-08-01" @default.
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- W2023781968 title "Vibrational analysis of the first ultraviolet band system of aniline" @default.
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