Electronic structures of 1-adamantanol, cyclohexanol and cyclohexanone and anisotropic interactions with He*(2³S) atoms: Collision-energy-resolved Penning ionization electron spectroscopy combined with quantum chemistry calculations

He I ultraviolet photoelectron spectra and He*(2³S) Penning ionization electron spectra have been measured for 1-adamantanol, cyclohexanol and cyclohexanone. Four stable isomeric conformers of cyclohexanol were predicted by Becke's three-parameter hybrid density functional B3LYP/6-31 + G(d,p) calculations. Since the orbital reactivity in Penning ionizations is simply related to the electron density extending outside the molecular surface, the theoretical Penning ionization electron spectra were synthesized using the calculated molecular orbital wave functions and ionization potentials. They were in good agreement with the experimental spectra except for the low-electron-energy bands. Collision energy dependence of partial ionization cross sections for the oxygen lone pair orbitals exhibited that there are strong steric hindrances by the neighboring hydrogen atoms in 1-adamantanol and cyclohexanol.