The radical cation of N,N-dimethylpiperazine
(DMP) has been studied using time-resolved optical
absorption and resonance Raman spectroscopy. Different
quantum-chemical methods were used to calculate
the molecular structures and vibrational force fields in the ground
state of the radical cation and in the resonant
excited state. An excellent agreement between theoretical and
experimental vibrational frequencies as well as
resonance Raman intensities could be achieved. It is concluded
that through-σ-bond interaction between the
formal lone pair on one amino nitrogen and the odd electron on the
other is strong enough to lead to a symmetric
charge-delocalized molecular structure of the DMP radical cation, with
a chair-type geometry.
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