Radical cation of N,N-dimethylpiperazine: dramatic structural effects of orbital interactions through bonds

The radical cation of N,N-dimethylpiperazine (DMP) was investigated since its molecule exhibited minimal splittings in the single pair ionization energies because of unfavorable geometry for orbital interactions through bonds. The molecule was studied utilizing time-resolved optical absorption and resonance Raman spectroscopy. It was established that an extensive geometry reorganization happened in DMP after ionization due to the negativity of the neutral molecular structure for through-bond interaction.