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Rigorous FC analysis revealed the precise structure of a cationic Chair-Ax-like conformer induced by removal of an electron from the lone-pair sp3 orbital of the nitrogen atom in piperidine. The adiabatic ionization energies of Chair-Eq and Chair-Ax conformers converting to a cationic state were determined to be 64 704 ± 4 cm-1 (8.0223 ± 0.0005 eV) and 64 473 ± 4 cm-1 (7.9936 ± 0.0005 eV), respectively. Consequently, the difference between their adiabatic ionization energies allowed the accurate determination of the conformational stabi
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